Preparation of poly(styrene‐co‐butyl acrylate)/montmorillonite nanocomposite by emulsion polymerization: Characterization and nanoscratch behavior

Organic–inorganic hybrid poly(styrene‐co‐butyl acrylate)/organically modified montmorillonite (PSBA/organo‐MMT) latex particles have been prepared by in situ emulsion polymerization. The effects of modifier variety and the level of organo‐MMT have been investigated on the basis of the characteristics and mechanical properties of the resulting hybrid emulsion polymers. Although the more hydrophilic intercalated organic modifiers increased the latex particle size, the hydrophobic ones decreased the particle size. A more heterogeneous copolymer chain intercalation was seen by widespread XRD reflection as the organo‐MMT (organoclay) level increases. The tapping mode atomic force microscopy (AFM) and transmission electron microscopy (TEM) were used to determine the dispersion state of organoclay particles inside the nanocomposite copolymer films. Dynamic mechanical thermal analysis (DMTA) showed that adding the organoclay to the copolymer decreased the maximum loss tangent (tanδ) value and caused the shift to a lower temperature. Interestingly, the incorporation of organoclay decreased the glass storage modulus of the copolymer, while increased the rubbery storage modulus to some extent. In addition, a standard indenter for the nanoscratching of copolymer nanocomposite films was used under low applied loads of 150 and 250 μN. The nanoscratch results showed that incorporation of a 3 wt % hydrophobic organoclay, e.g., Closite15A, in the copolymer matrix enhanced considerably the near‐surface hardness and grooving resistance of the nanocomposite film at room temperature. In fact, copolymer nanocomposite films with higher near‐surface hardness and tanδ curve broadening exhibited more nanoscratch resistance through a specific variety of viscoelastic deformation, which did not create a bigger groove. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation of hemispherical poly(4‐vinylpyridine‐co‐butyl acrylate)/poly(styrene‐co‐butyl acrylate) composite microspheres by seeded preswelling emulsion polymerization

Seeded preswelling emulsion polymerization was carried out by using monodispersed poly(4‐vinylpyridine‐co‐butyl acrylate) [P(4VP‐BA)] particles as the seed, and styrene and butyl acrylate as the second‐stage monomers under different polymerization conditions, to obtain hemispherical polystyrene (PST)‐rich–P4VP‐rich microspheres. Prior to polymerization, toluene was added into the preswelling system together with the second‐stage monomers. It was found that, with the increase of the amount of toluene, the particle morphology showed a tendency toward desirable hemispherical structure, and the colloidal stability of composite latex was improved. When the weight ratio of toluene/seed latex was increased up to 7.5/40 (g/g), the stable hemispherical latex could be obtained. However, when toluene was not added, the coagulum formed on the wall of the reactor during polymerization, and the composite particles with multiple surface domains (such as sandwich‐like, popcorn‐like) were formed. In addition, the final morphology of composite particles was influenced by the polarity of the seed crosslinker and the hydrophilicity of the second‐stage initiator, which could affect the mobility of poly(styrene‐co‐butyl acrylate) [P(ST‐BA)] chains. The morphology development during the polymerization was investigated in detail, and a schematic model was derived to depict the formation mechanism of hemispherical P(4VP‐BA)/P(ST‐BA) composite microspheres. The results revealed that the mobility of the P(ST‐BA) chains influenced the diffusion of the P(ST‐BA) domains on the surface of the P(4VP‐BA) matrix. When the mobility of the P(ST‐BA) chains allowed small‐size P(ST‐BA) domains to coalesce into one larger domain, complete phase‐separated morphology (hemisphere) could be achieved. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3811–3821, 2003     

Study on synthesis and morphology control of poly(4‐vinylpyridine‐co‐butyl acrylate)/poly(styrene‐co‐butyl acrylate) composite microspheres

Monodispersed crosslinked cationic poly(4‐vinylpyridine‐co‐butyl acrylate) [P(4VP‐BA)] seed latexes were prepared by soapless emulsion polymerization, using 2,2′‐azobismethyl(propionamidine)dihydrochloride (V₅₀) as an initiator and divinylbenzene (DVB) or ethylene glycol dimethacrylate (EGDMA) as a crosslinker. The optimum condition to obtain monodispersed stable latex was investigated. It was found that the colloidal stability of the P4VP latex can be improved by adding an adequate amount of BA (BA/4VP = 1/4, w/w), and adopting a semicontinuous monomer feed mode. Subsequently, poly(4‐vinylpyridine‐co‐butyl acrylate)/Poly(styrene‐co‐butyl acrylate) [P(4VP‐BA)/P(ST‐BA)] composite microspheres were synthesized by seeded polymerization, using the above latex as a seed and a mixture of ST and BA as the second‐stage monomers. The effects of the type of crosslinker, the degree of crosslinking, and the initiators (AIBN and V₅₀) on the morphology of final composite particles are discussed in detail. It was found that P(4VP‐BA)/P(ST‐BA) composite microspheres were always surrounded by a PST‐rich shell when V₅₀ was used as initiator, while sandwich‐like or popcorn‐like composite particles were produced when AIBN was employed. This is because the polarity of the polymer chains with AIBN fragments is lower than for the polymer with V₅₀ fragments, hence leading to higher interfacial tension between the second‐stage PST‐rich polymer and the aqueous phase, and between PST‐rich polymer and P4VP‐rich seed polymer. As a result, the seed cannot be engulfed by the PST‐rich polymer. Furthermore, the decrease of T_g of the second‐stage polymer promoted phase separation between the seeds and the PST‐rich polymer: sandwich‐like particles formed more preferably than popcorn‐like particles. It is important knowledge that various morphologies different from PST‐rich core/P4VP‐rich shell morphology, can be obtained only by changing the initiator, considering P4VP is much more hydrophilic than PST. The zeta potential of composite particles initiated by AIBN in seeded polymerization shifted from a positive to a negative charge. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1190–1203, 2002     

Use of clay-anchored reactive modifier for the synthesis of poly (styrene-co-butyl acrylate)/clay nanocomposite via in situ AGET ATRP

Atom transfer radical polymerization using activators generated by electron transfer (AGET ATRP) was employed to synthesize well-defined poly (styrene-co-butyl acrylate)/clay nanocomposites. Dodecyltrimethylammonium bromide (DDTMAB) and Vinylbenzyltrimethylammonium chloride (VBTMAC) surfactants were used as clay modifier. The classical surfactant is used to expand the interlayer gallery of montmorillonite; however, double bond of reactive modifier participates in chain propagation process and forms clay-attached polymer chains. Subsequently synthesis of attached and free poly (styrene-co-butyl acrylate) chains and their composition was confirmed by Fourier-transform infrared spectroscopy (FTIR) and proton nuclear magnetic resonance spectroscopy (¹H NMR). Narrow distribution of nanocomposites molecular weight was confirmed by gel permeation chromatography (GPC). Partially exfoliated clay layers in the copolymer matrix were revealed by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Thermal properties of the nanocomposites were evaluated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Thermal decomposition of the nanocomposites was hindered in the presence of nanoclay. Dynamic mechanical thermal analysis (DMTA) results show that addition of nanoclay was also resulted in enhanced storage modulus (E′) in comparison with the neat copolymer. Lower glass transition temperature of nanocomposites was displayed by DSC.     

Supermicron poly(butyl acrylate)/polystyrene core-shell latexes

Latex particles of up to 2 μm can be made by standard emulsion polymerization methods, but attempts at larger sizes usually results in a crop of smaller particles or coagulation of the latex. In this work, it is shown that use of an oil-soluble initiator (2,2′ azodiisobutyronitrile [AIBN]) provides a means by which large (6 μm diameter) polybutyl acrylate latex particles can be made by sequential core-shell polymerizations. It is suggested that the limited water solubility of AIBN decreases the formation of secondary particles and that the lower ionic strength of the water phase enhances stability of the latex compared to a conventional persulfate initiator. To further minimize formation of secondary particles, long reaction times and progressively larger proportions of seed latex are used in successive reactions. © 1992 John Wiley & Sons, Inc.     

Preparation of poly(styrene‐co‐hexylacrylate)/cellulose whiskers nanocomposites via miniemulsion polymerization

A stable aqueous nanocomposite dispersion containing cellulose whiskers and a poly(styrene‐co‐hexylacrylate) matrix was prepared via miniemulsion polymerization. We were able to prepare a stable dispersion with a 20 wt % solid content and a cellulose whiskers content ranging from 1 up to 5 wt % based on polymer content. To avoid particle agglomeration leading to coagulum formation, the addition of a low amount of reactive silane, i.e., methacryloxypropyl triethoxysilane revealed to efficiently stabilize the dispersion. The nanocomposite dispersion was characterized using dynamic light scattering, transmission electron microscopy, and atomic force microscopy. Films obtained by casting followed by water evaporation and particle coalescence were analyzed by differential scanning calorimetry, dynamic mechanical analysis, and tensile testing. At 5 wt % whiskers loading, an enhancement by 500% of the storage modulus above the glass transition was determined. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Influence of granulometry and organic treatment of a Brazilian montmorillonite on the properties of poly(styrene‐co‐n‐butyl acrylate)/layered silicate nanocomposites prepared by miniemulsion polymerization

The influence of granulometry and organic treatment of a Brazilian montmorillonite (MMT) clay on the synthesis and properties of poly(styrene‐co‐n‐butyl acrylate)/layered silicate nanocomposites was studied. Hybrid latexes of poly(styrene‐co‐butyl acrylate)/MMT were synthesized via miniemulsion polymerization using either sodium or organically modified MMT. Five clay granulometries ranging from clay particles smaller than 75 μm to colloidal size were selected. The size of the clay particles was evaluated by specific surface area measurements (BET). Cetyl trimethyl ammonium chloride was used as an organic modifier to enhance the clay compatibility with the monomer phase before polymerization and to improve the clay distribution and dispersion within the polymeric matrix after polymerization. The sodium and organically modified natural clays as well as the composites were characterized by X‐ray diffraction analysis. The latexes were characterized by dynamic light scattering. The mechanical, thermal, and rheological properties of the composites obtained were characterized by dynamical‐mechanical analysis, thermogravimetry, and small amplitude oscillatory shear tests, respectively. The results showed that smaller the size of the organically modified MMT, the higher the degree of exfoliation of nanoplatelets. Hybrid latexes in presence of Na‐MMT resulted in materials with intercalated structures. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Complexation of poly(dimethylsiloxane)/poly(methyl methacrylate‐co‐butyl acrylate‐co‐methacrylic acid) latex with poly(dimethylsiloxane)/poly(vinyl acetate‐co‐butyl acrylate) latex

Two latices—the poly(dimethylsiloxane) (PDMS)/poly(methyl methacrylate‐co‐butyl acrylate‐co‐methacrylic acid) system (PA latex) and the PDMS/poly(vinyl acetate‐co‐butyl acrylate) system (PB latex)—were prepared by seeded emulsion polymerization, and PA/PB complex latices were obtained through the interparticle complexation of the PA latex with the PB latex. In addition, for the further study of the interparticle complexation of the PA latex with the PB latex, copolymer latices [PDMS/methyl methacrylate‐co‐butyl acrylate‐co‐vinyl acetate‐co‐methacrylic acid) (PC)] were prepared according to the monomer recipe of the complex latices and the polymerization process of the component latices. The properties of the obtained polymer latices and complex latices were investigated with surface‐tension, contact‐angle, and viscosity measurements. The mechanical properties of the coatings obtained from the latices were investigated with tensile‐strength measurements. The results showed that, in comparison with the two component latices (PA latex and PB latex) and the corresponding copolymer latices (PC latices), the PA/PB complex latices had lower surface tension, lower viscosities, and better wettability to different substrates. The tensile strengths of the coatings obtained from the complex latices were higher than the tensile strengths of the coatings from the two component latices and copolymer latices. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2522–2527, 2004     

Synthesis and characterization of poly(butyl acrylate)/silica and poly(butyl acrylate)/silica/poly(methyl methacrylate) composite particles

Poly(butyl acrylate)/poly(methyl methacrylate) (PBA/PMMA) core–shell particles embedded with nanometer‐sized silica particles were prepared by emulsion polymerization of butyl acrylate (BA) in the presence of silica particles preabsorbed with 2,2′‐azobis(2‐amidinopropane)dihydrochloride (AIBA) initiator and subsequent MMA emulsion polymerization in the presence of PBA/silica composite particles. The morphologies of the resulting PBA/silica and PBA/silica/PMMA composite particles were characterized, which showed that AIBA could be absorbed effectively onto silica particles when the pH of the dispersion medium was greater than the isoelectric potential point of silica. The critical amount of AIBA added to have stable dispersion of silica particles increased as the pH of the dispersion medium increased. PBA/silica composite particles prepared by in situ emulsion polymerization using silica preabsorbed with AIBA showed higher silica absorption efficiency than did the PBA/silica composite particles prepared by direct mixing of PBA latex and silica dispersion or by emulsion polymerization in which AIBA was added after the mixing of BA and silica. The PBA/silica composite particles exhibited a raspberrylike morphology, with silica particles “adhered” to the surfaces of the PBA particles, whereas the PBA/silica/PMMA composite latex particles exhibited a sandwich morphology, with silica particles mainly at the interface between the PBA core and the PMMA shell. Subsequently, the PBA/silica/PMMA composite latex obtained had a narrow particle size distribution and good dispersion stability. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3425–3432, 2006     

Preparation and properties of poly(silicone‐co‐acrylate)/montmorillonite nanocomposite emulsion

Poly (silicone‐co‐acrylate)/montmorillonite nanocomposite emulsion were prepared by in situ intercalative emulsion polymerization of acrylate and organosilicone, in the presence of organic modified montmorillonite (OMMT) with different OMMT contents (0, 0.5, 1, 1.5, and 2 wt %). The nanocomposite emulsions were characterized with X‐ray diffraction (XRD), laser light scattering, fourier transform infrared (FTIR), rheological measurements, surface tension, drying speed, and water absorption property. Results showed that OMMT could improve the properties of emulsion, in other words, the properties of nanocomposite emulsion were better when compared with those of the silicone–acrylate emulsion. The properties of nanocomposite emulsion containing 1 wt % OMMT was the best one, and obtained the following advantages: smaller particle size, faster drying speed, shorter curing time, smaller surface tension, bigger apparent viscosity, and improved resistant water by the incorporation of OMMT. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3963–3970, 2006     

Specific interactions in poly(styrene‐co‐2‐hydroxyethyl acrylate)/poly(styrene‐co‐N,N‐dimethylacrylamide) systems

Amphiphilic copolymers of poly(styrene‐co‐2‐hydroxyethyl acrylate) (SHEA) and poly(styrene‐co‐N, N‐dimethylacrylamide) (SAD) of different compositions were prepared by free radical copolymerization and characterized by different techniques. Depending on the nature of the solvent and the densities of interacting species incorporated within the polystyrene matrices, novel materials as blends or interpolymer complexes with properties different from those of their constituents were elaborated when these copolymers are mixed together. The specific interpolymer interactions of hydrogen bonding type and the phase behavior of the elaborated materials were investigated by differential scanning calorimetry (DSC) and Fourier transform infra red spectroscopy (FTIR). The specific interactions of hydrogen bonding type that occurred within the SHEA and within their blends with the SAD were evidenced by FTIR qualitatively by the appearance of a new band at 1626 cm^?1 and quantitatively using appropriate spectral curve fitting in the carbonyl and amide regions. The variation of the glass transition temperature with the blend composition behaved differently with the densities of interacting species. The thermal degradation behavior of the materials was studied by thermogravimetry. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of poly(butyl acrylate‐co‐methyl methacrylate)/montmorillonite waterborne nanocomposite via semibatch emulsion polymerization

Poly(butyl acrylate‐co‐methyl methacrylate)‐montmorillonite (MMT) waterborne nanocomposites were successfully synthesized by semibatch emulsion polymerization. The syntheses of the nanocomposites were performed in presence of sodium montmorillonite (Na‐MMT) and organically modified montmorillonite (O‐MMT). O‐MMT was used directly after the modification of Na‐MMT with dimethyl dioctadecyl ammonium chloride. Both Na‐MMT and O‐MMT were sonified to obtain nanocomposites with 47 wt % solids and 3 wt % Na‐MMT or O‐MMT content. Average particle sizes of Na‐MMT nanocomposites were measured as 110–150 nm while O‐MMT nanocomposites were measured as 200–350 nm. Both Na‐MMT and O‐MMT increased thermal, mechanical, and barrier properties (water vapor and oxygen permeability) of the pristine copolymer explicitly. X‐ray diffraction and transmission electron microscope studies show that exfoliated morphology was obtained. The gloss values of O‐MMT nanocomposites were found to be higher than that of the pristine copolymer. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42373.     

Synthesis and characterization of novel oligomeric poly(styrene‐co‐acrylonitrile)–clay complexes

Oligomeric poly(styrene‐co‐acrylonitrile) quaternary ammonium salts were prepared through reactions of trimethylamine with corresponding poly(styrene–acrylonitrile–vinyl benzyl chloride)s, which were synthesized by the free‐radical polymerization of a mixture of styrene, acrylonitrile, and vinyl benzyl chloride. Then, oligomeric poly(styrene‐co‐acrylonitrile)‐modified clays were prepared through the cation exchange of the sodium ions in the clay with the corresponding poly(styrene‐co‐acrylonitrile) quaternary ammonium salts. The poly(styrene–acrylonitrile–vinyl benzyl chloride)s, poly(styrene‐co‐acrylonitrile) quaternary ammonium salts, and their clay complexes were characterized with infrared spectroscopy, gel permeation chromatography, thermogravimetric analysis, proton nuclear magnetic resonance, X‐ray diffraction, and transmission electron microscopy. X‐ray diffraction and transmission electron microscopy studies showed that these novel clay complexes were well intercalated. Furthermore, thermogravimetric analysis data indicated that this series of polymerically modified clays had high enough thermal stability for nanocomposites by melt blending. The thermal treatment of one of these novel clays at 250°C under nitrogen was also conducted. Solubility and infrared studies of this thermally treated clay complex revealed that a novel polyimine/enamine structure clay complex had been formed in the gallery of the clay. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Morphology of poly(butyl acrylate)/poly(styrene‐co‐methyl methacrylate) latex prepared by starved emulsion polymerization: II. Development of particle morphology

Heterogeneous latexes were prepared by a two‐stage seeded emulsion polymerization process under monomer starved conditions at 80 °C using potassium persulfate as the initiator and sodium dodecyl sulfate as the emulsifier. Poly(butyl acrylate) latexes were used as seeds. The second‐stage polymer was poly(styrene‐co‐methyl methacrylate). By varying the amount of methyl methacrylate (MMA) in the second‐stage copolymer, the polarity of the copolymer phase could be controlled. It was found that the latex particles displayed different morphologies depending on the monomer ratio. The amount of MMA had a significant effect on the evolution of morphology. The morphologies were observed by transmission electron microscopy. In addition, the evolution of the particle morphology was predicted by the mathmatical model for cluster migration. The model gave the same trends as the experimental results. © 2002 Society of Chemical Industry     

Synthesis and characterization of exfoliated poly(styrene‐co‐methyl methacrylate) nanocomposite via miniemulsion atom transfer radical polymerization: an activators generated by electron transfer approach

Exfoliated poly(styrene‐co‐methyl methacrylate) nanocomposites were synthesized using activators generated by electron transfer for atom transfer radical polymerization (AGET ATRP). Miniemulsion polymerization was used for its abundant advantages to encapsulate inorganic materials and eliminate organic solvents from products for environmentally friendly purposes. Cetyltrimethylammonium bromide (CTAB) as a cationic surfactant, which is an effective surfactant at higher temperatures, was used to stabilize the miniemulsion system. Successful miniemulsion AGET ATRP was carried out by using 4,4'‐dinonyl‐2,2'‐bipyridine (dNbPy) as a hydrophobic ligand. Formation of monodispersed droplets and particles with sizes in the range of 200nm was examined by dynamic light scattering (DLS). Conversion and molecular weight study were also carried out using gravimetry and gel permeation chromatography, respectively. By adding clay content, a decrease in the conversion and molecular weight of the nanocomposites are observed. However, an increase in the PDI values of nanocomposites was observed by the addition of nanoclay content. Thermogravimetric analysis results demonstrate that thermal stability of all the nanocomposites in comparison with the neat copolymer increases. Differential scanning calorimetry results show that T_g decreases by increasing clay content. Monodisperse distribution of spherical shape particles with sizes in the range of ∼ 200 nm was demonstrated by using scanning electron microscopy images of nanocomposite containing 1 wt% of nanoclay, which is more compiled with DLS results. Transmission electron microscopy results shows well‐dispersed exfoliated clay layers in the polymer matrix of PSMNM 1, which is coincidence with X‐ray diffraction data. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Preparation and electrorheological characterization of suspensions of poly(urethane acrylate)/clay nanocomposite particles

Micron‐sized poly(urethane acrylate) (PUA)/clay nanocomposite particles were synthesized by suspension polymerization. UA containing a poly(ethylene oxide) group in the main chain was first inserted into the silicate layers of montmorillonite clay through mixing the UA with the clay. Then, ethylene glycol dimethacrylate and an oil‐soluble initiator were added into this UA/clay mixture, followed by the emulsification of the monomer mixture in an aqueous solution of polymeric stabilizer. Suspension polymerization was carried out at 60°C for 12 h to obtain the PUA/clay composite particles. The incorporation of clay into the polymer phase was verified by FTIR spectroscopy, and the intercalation structure of the clay composite was confirmed by X‐ray diffraction analysis. Other characterizations including thermal analysis, morphological observation, and dielectric analysis were also performed. After suspensions of bare PUA and PUA/clay nanocomposite particles in silicone oil were prepared, their electrorheological properties were measured under various electric fields and compared. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 458–464, 2003     

Preparation and properties of poly[styrene‐co‐(butyl acrylate)‐co‐(acrylic acid)]/silica nanocomposite latex prepared using an acidic silica sol

BACKGROUND: Polyacrylate/silica nanocomposite latexes have been fabricated using blending methods with silica nanopowder, in situ polymerization with surface‐functionalized silica nanoparticles or sol–gel processes with silica precursors. But these approaches have the disadvantages of limited silica load, poor emulsion stability or poor film‐forming ability. RESULTS: In this work, poly[styrene‐co‐(butyl acrylate)‐co‐(acrylic acid)] [P(St‐BA‐AA)]/silica nanocomposite latexes and their dried films were prepared by adding an acidic silica sol to the emulsion polymerization stage. Morphological and rheological characterization shows that the silica nanoparticles are not encapsulated within polymer latex particles, but interact partially with polymer latex particles via hydrogen bonds between the silanol groups and the ? COOH groups at the surface of the polymer particles. The dried nanocomposite films have a better UV‐blocking ability than the pure polymer film, and retain their transparency even with a silica content up to 9.1 wt%. More interestingly, the hardness of the nanocomposite films increases markedly with increasing silica content, and the toughness of the films is not reduced at silica contents up to 33.3 wt%. An unexpected improvement of the solvent resistance of the nanocomposite films is also observed. CONCLUSION: Highly stable P(St‐BA‐AA)/silica nanocomposite latexes can be prepared with a wide range of silica content using an acidic silica sol. The dried nanocomposite films of these latexes exhibit simultaneous improvement of hardness and toughness even at high silica load, and enhanced solvent resistance, presumably resulting from hydrogen bond interactions between polymer chains and silica particles as well as silica aggregate/particle networks. Copyright © 2009 Society of Chemical Industry     

Enhancement of dispersion of carbon nanotube and physical properties of poly(styrene‐co‐acrylonitrile)/multiwalled carbon nanotube nanocomposite via surface initiated ATRP

Dispersion behavior of multiwalled carbon nanotube (MWCNT), rheological and mechanical properties of various MWCNT/poly(styrene‐co‐acrylonitrile) (SAN) nanocomposites were investigated. MWCNT/SAN nanocomposites were prepared by three different methods; MWCNT/SAN melt blending, MWCNT/SAN in situ atom transfer radical polymerization (ATRP) and functionalized‐MWCNT/SAN in situ ATRP. Formation of SAN onto the surface of MWCNT and the molecular weight of grafted‐SAN were confirmed by fourier transform infrared spectra, ¹H‐NMR and ¹³C‐NMR. Crossover frequency of storage and loss modulus from rheological measurement and dynamic mechanical analysis showed that functionalized MWCNT/SAN in situ ATRP nanocomposite showed more uniform dispersion of MWCNT. Improved mechanical and electrical properties were observed for functionalized MWCNT/SAN in situ ATRP nanocomposite. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of poly(styrene‐co‐maleic anhydride) imidization on the miscibility and phase‐separation temperatures of poly(styrene‐co‐maleic anhydride)/poly(vinyl methyl ether) and poly(styrene‐co‐maleic anhydride)/ poly(methyl methacrylate) blends

The objective of this work was to study the miscibility and phase‐separation temperatures of poly(styrene‐co‐maleic anhydride) (SMA)/poly(vinyl methyl ether) (PVME) and SMA/poly(methyl methacrylate) (PMMA) blends with differential scanning calorimetry and small‐angle light scattering techniques. We focused on the effect of SMA partial imidization with aniline on the miscibility and phase‐separation temperatures of these blends. The SMA imidization reaction led to a partially imidized styrene N‐phenyl succinimide copolymer (SMI) with a degree of conversion of 49% and a decomposition temperature higher than that of SMA by about 20°C. We observed that both SMI/PVME and SMI/PMMA blends had lower critical solution temperature behavior. The imidization of SMA increased the phase‐separation temperature of the SMA/PVME blend and decreased that of the SMA/PMMA blend. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of initiator on morphology in poly(vinyl acetate)/polystyrene and poly(butyl acrylate)/polystyrene composite latexes

Summary A simple method of related sensitivity range to predict thermodynamic equilibrium morphology of a core-shell latex particle (J Appl Polym Sci. 2004, 92, 3144), is recently explored. The article proposed that it is necessary to classify core-shell latex systems as sensitivity and no-sensitivity by their equilibrium morphology sensitivity to initiator and emulsifier. As for the sensitivity system, the final morphology may change by adjusting initiator and emulsifier, whereas, for the no-sensitivity system, it is hard to change its final morphology in this way. Equilibrium morphologies in system poly(vinyl acetate) (PVAc)/polystyrene (PSt) and poly(butyl acrylate) (PBA)/ PSt composite latexes particles were observed by changing initiator. Composite latexes of the two systems were synthesized by two-stage semi-continuous emulsion polymerization. The types or/and concentration of initiator changed in two stages in which the oil-soluble initiator 2,2-azobis(isobutyronitrile) (AIBN) and the water-soluble initiator potassium persulfate (KPS) were used respectively, the concentration of which was 0.5% or 2% based on the weight of monomer. The results showed that the two systems had different characteristics. At different experiment conditions designed, the same equilibrium morphologies with PSt as core and PVAc as shell were obtained in system PVAc/PSt, whereas, three different equilibrium morphologies, core-shell, inverted core-shell and hemisphere, were obtained in system PBA/PSt. The equilibrium morphology in system PVAc/PSt is no-sensitive to initiator, and the equilibrium morphology in system PBA/PSt is sensitive to initiator.