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     

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     

Structure and properties of tailor‐made poly(ethyl acrylate)/clay nanocomposites prepared by in situ atom transfer radical polymerization

An in‐depth study was carried out on the structure and properties of a series of poly(ethyl acrylate)/clay nanocomposites prepared by in situ atom transfer radical polymerization (PNCIs) with well‐defined molecular weights and narrow molecular weight distributions. Wide‐angle X‐ray diffraction and transmission electron microscopy studies revealed an exfoliated clay morphology, whereas conventional solution blending generated an intercalated structure. The storage moduli of the PNCIs showed a moderate increase over that of the neat polymer [poly(ethyl acrylate)]. The sample containing 4 wt % clay (PNCI4, where the number following PNCI indicates the weight percentage of clay) exhibited the highest improvement (31.9% at 25°C). In PNCIs, the β‐transition temperature showed a remarkable decrease (by 175% in PNCI4) along with a shift toward higher temperatures. This indicated the probability of the anchoring of the ? OH group of the clay layers to the >C?O group of the pendant acrylate moiety, which was also confirmed by Fourier transform infrared analysis. Rheological measurements indicated a significant increase in the shear viscosity [by 9% in PNCI2, 15% in PNCI4, and 6% in the poly(ethyl acrylate)/clay nanocomposite with 2 wt % clay prepared by solution blending]. The PNCIs registered enhanced thermal stability, as indicated by the shift in the peak maximum temperature (388 and 392°C for the neat polymer and PNCI4, respectively) and a decrease in the rate of degradation (by 3.5% in PNCI2, 10.2% in PNCI4, and 49.3% in PNCI6). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Highly exfoliated poly(ϵ‐caprolactone)/organomontmorillonite nanocomposites prepared by in situ polymerization

Ethylene–propylene–diene rubbers (EPDM) with 2-ethylidene-5-norbornene (ENB), dicyclopentadiene (DCPD), and 1,4-hexadiene (HD) as third monomers have been vulcanized with peroxide and with a conventional sulfur vulcanization recipe, and their devulcanization was subsequently investigated for recycling purposes. The behavior of these vulcanizates during pure thermal devulcanization depends on the EPDM third monomer and the crosslinker used. Peroxide vulcanizates of ENB-EPDM devulcanize only to a small extent and predominantly by random scission, whereas peroxide vulcanizates of HD-EPDM devulcanize by crosslink scission. In contrast, sulfur vulcanizates of ENB-EPDM, devulcanize mainly by crosslink scission. During devulcanization of sulfur-cured HD-EPDM, scission of both crosslinks and main chains occurs. Sulfur-cured DCPD-EPDM cannot be devulcanized but shows further crosslinking instead. In those cases, where purely thermal devulcanization is already effective to a certain extent, diphenyldisulfide as devulcanization agent increases the effectivity during thermochemical devulcanization. Hexadecylamine as an alternative devulcanization agent is effective for ENB-EPDM but does not contribute to thermochemical devulcanization of HD-EPDM. In summary, devulcanization proceeds by different mechanisms in ENB-EPDM, DCPD-EPDM, and HD-EPDM. Explanations are given in terms of the chemical structures of the third monomers, the corresponding crosslinks, and devulcanization agents. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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     

Biodegradation of poly(butylene adipate‐co‐butylene terephthalate)/layered‐silicate nanocomposites

The biodegradability of poly(butylene adipate‐co‐butylene terephthalate) (PBAT) and PBAT/starch composites with layered silicates prepared by melt intercalation was evaluated with aerobic biodegradability tests in soil and in an aqueous medium containing activated sludge. Nonmodified montmorillonite (MMT) and octadecylamine‐modified montmorillonite (ODA‐M), known to give a microcomposite and an intercalated nanocomposite for PBAT, respectively, were used as layered silicates. After they were buried in the soil for 8 months, the PBAT/MMT microcomposite exhibited a higher weight loss than the control PBAT, whereas the PBAT/ODA‐M nanocomposite showed a lower weight loss instead. Also, the biodegradability test in the aqueous medium, by determining the biochemical oxygen demand, showed that the addition of MMT and/or starch to PBAT promoted biodegradation, whereas the addition of ODA‐M did not. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

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     

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     

Synthesize and characterization of styrene‐N‐phenyl maleimide/montmorillonite nanocomposites prepared through emulsion polymerization

Composites of organomodified (OMMT) and pristine montmorillonite (MMT) intercalated by styrene‐N‐phenyl maleimide (PMI) copolymer were prepared by emulsion intercalative polymerization. X‐ray diffraction (XRD) and transmission electron microscopy results show that the dispersability of clay in the matrix was greatly improved by the incorporation of polar moiety PMI. The dispersability of OMMT in the matrix is better than MMT. XRD patterns of the extracted nanocomposites showed that d₀₀₁ of the clay are much larger than that of the original OMMT and MMT, which indicates that the interaction of copolymer with the clay layers was greatly improved by incorporation with polar monomer PMI. The thermal property of the composites was greatly improved by the intercalation with clay. The DSC results showed that the glass transition of the composites became inconspicuous, which indicated that the movement of the polymer segment was extremely confined by the clay layer. The consistency factor of the melts of the composites increased monotonically with a decreasing flow index showing stronger shear thinning property of the composites. The rheological activity energy of the composites decreased more than that of the pure copolymer. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1010–1015, 2005     

Poly (styrene‐n‐butyl acrylate‐methyl methacrylate)/silica nanocomposites prepared by emulsion polymerization

Poly (styrene‐n‐butyl acrylate‐methyl methacrylate) (PSBM)/silica nanocomposite was prepared by emulsion polymerization in the presence of oleic acid surface modified nanosilica. The structure, morphology, size, and size distribution were characterized by Fourier transform infrared (FTIR), transmission electron microscopy (TEM), and dynamics laser scattering. The chemical bond was formed between PSBM and nanosilica revealed by FTIR and TEM studies. The composite particles with an averaged diameter ranging from 30 to 80 nm have the core‐shell structure. The effect of silica content on the glass transition temperature T_g, pyrolyze temperature, and rheological behavior of PSBM composites was systematically investigated. The results indicated that the addition of nanosilica could effectively inhibit chain movement, and improved the pyrolyze temperature of PSBM. The steady viscosity and dynamic modulus were strongly dependent on the content and distribution of nanosilica in PSBM nanocomposites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

In situ preparation and properties of high‐solid‐content and low‐viscosity poly(methyl methacrylate/n‐butyl acrylate/acrylic acid)/poly(styrene/acrylic acid) composite latexes

With monodispersed poly(methyl methacrylate/n‐butyl acrylate/acrylic acid) [P(MMA/BA/AA)] seeded latex with a particle size of 485 nm and a solid content of 50 wt % as a medium, a series of stable P(MMA/BA/AA)/poly(styrene/acrylic acid) composite latexes with a high solid content (70 wt %) and low viscosities (500–1000 mPa · s when the shear rate was 21 s^?1) was prepared in situ via simple two‐step semicontinuous monomer adding technology. The coagulum ratio of polymerization was about 0.05 wt %. The particle size distribution of such latexes was bimodal, in which the large particle was about 589 nm and the small one was about 80 nm. The latexes combined good mechanical properties with good film‐forming properties. Differential scanning calorimetry showed that the corresponding latex film had a two‐phase structure. The morphology of the latex film was characterized with atomic force microscopy and scanning electron microscopy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1815–1825, 2007     

Synthesis and characterization of poly(styrene‐co‐butyl acrylate)/clay nanocomposite latexes in miniemulsion by AGET ATRP

Polymer/clay nanocomposite latexes in the form of positively charged nanoparticles were synthesized by a newly developed initiating system, activators generated by electron transfer (AGET), which has been employed in atom transfer radical polymerization (ATRP). These clay‐dispersed latexes were synthesized using AGET ATRP of styrene and butyl acrylate in a miniemulsion system in which, ascorbic acid as a reducing agent was added drop wise to reduce termination reactions. Particle size and particle size distribution of resulted nanocomposite latexes were characterized by dynamic light scattering (DLS). These latexes were in the range of 138 to 171 nm in size. Gel permeation chromatography (GPC) was used to characterize the molecular weight and molecular weight distribution of the resultant copolymer nanocomposites. GPC traces showed that polymers of narrow molecular weight distribution and low Polydispersity Index (PDI) have been synthesized; this clearly shows ATRP reaction is conducted successfully. By increasing nanoclay content, molecular weight of the nanocomposites decreases. The presence of the nanofiller increases the thermal stability of the nanocomposites as investigated by thermogravimetric Analysis (TGA). Glass transition temperature of nanocomposites increases compared with the neat copolymer which was studied by differential scanning calorimetry (DSC). scanning electron microscope (SEM) showed sphere morphology of polymer particles synthesized by miniemulsion polymerization. X‐ray diffraction (XRD) and transmission electron microscopy (TEM) results showed that mixed intercalated and exfoliated morphology is obtained. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Characteristics of polystyrene/organoclay nanocomposites prepared by in‐situ polymerization with macroazoinitiator containing poly(dimethylsiloxane) segment

Polystyrene (PS)/organoclay nanocomposites were prepared by the in situ polymerization of styrene in the presence of organoclay with macroazoinitiator (MAI), composed of repeated sequences of poly(dimethylsiloxane) (PDMS) and azo groups. The X‐ray diffraction patterns and the morphology observed with a transmission electron microscope showed that the dispersion of organoclay in polymer matrix improved as the content of the PDMS segment in the nanocomposite increased. However, negative effects on the rise of glass transition temperatures and the thermal resistance of nanocomposite, measured by differential scanning calorimetry and thermogravimetry, at a high content of the PDMS segment, suggested that organoclay lay preferentially in the PDMS domain. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 2841–2847, 2006     

Structure and properties of polybutadiene/montmorillonite nanocomposites prepared by in situ polymerization

Polybutadiene (PB)/Montmorillonite nanocomposites (NCs) were prepared by in situ polymerization through the anionic polymerization technique. The effects of treating method of organophilic MMT (OMMT), the type of OMMT, and the solvent used in polymerization were studied. The structure and properties of NCs were characterized using X‐ray Diffraction (XRD), transmission electron micrograph (TEM), H‐NMR spectrum, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dynamic mechanical analysis (DMA). The consumption of BuLi was varied with different treating methods. The molecular weight distribution of PB added with OMMT (DK1) was wide, and the molecular weight distribution became narrow when OMMT‐DK1B and DK4 were added. OMMT did not disperse stably in cyclohexane, but could form a homogeneous solution in toluene and xylene. XRD and TEM showed that exfoliated NCs were obtained by in situ polymerization through the anionic polymerization technique. From the H‐NMR spectrum of PB and PB/OMMT NCs, it could be seen that the content of 1, 2 units of PB increased ～100%, while 1, 4 units decreased when 6.2 wt % of OMMT was added. The results of DSC and DMA indicated that T_g and T_dc were increased when compared with those of PB. Both storage modulus and loss modulus were increased with the addition of OMMT, and tan δ was decreased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3615–3621, 2006     

Encapsulation of titanium dioxide in styrene/n‐butyl acrylate copolymer by miniemulsion polymerization

Miniemulsion copolymerization of styrene/n‐butyl acrylate was investigated as a means of encapsulating hydrophilic titanium dioxide (TiO₂) in a film‐forming polymer. Dispersion studies of the TiO₂ were first carried out to determine the choice of stabilizer, its concentration, and the dispersion process conditions for obtaining stable TiO₂ particles with minimum particle size. Through screening studies of various functional stabilizers and shelf‐life stability studies at both room and polymerization temperatures, Solsperse 32,000 was selected to give relatively small and stable TiO₂ particles at 1 wt % stabilizer and with 20–25 min sonification. The subsequent encapsulation of the dispersed TiO₂ particles in styrene/n‐butyl acrylate copolymer (St/BA) via miniemulsion polymerization was carried out and compared with a control study using styrene monomer alone. The lattices resulting from the miniemulsion encapsulation polymerizations were characterized in terms of the encapsulation efficiencies (via density gradient column separations; DGC) and particle size (via dynamic light scattering). Encapsulation efficiencies revealed that complete encapsulation of all of the TiO₂ by all of the polymer was not achieved. The maximum encapsulation efficiencies were 79.1% TiO₂ inside 61.7% polystyrene and 63.6% TiO₂ inside 38.5% St/BA copolymer. As the density of the particles collected from the DGC increased from one layer to another, both the average particle size and the number of the TiO₂ particles contained in each latex particle increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3479–3486, 2006     

Synthesis and characterization of poly(methyl methacrylate)/montmorillonite nanocomposites by in situ bulk polymerization

Poly(methyl methacrylate)/montmorillonite (MMT) nanocomposites were prepared by in situ bulk polymerization. The results showed that the silicone coupling agent affected the structure and properties of hybrid materials. XRD analysis showed that the dispersion of clay in nanocomposites with silicone‐modified organophilic MMT was more ordered than that in nanocomposites with unmodified organophilic MMT. The glass transition temperature (T_g) of the nanocomposites was 6–15°C higher and the thermal decomposition temperature (T_d) was 100–120°C higher than those of pure PMMA. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2256–2260, 2003     

Phase separation behavior and morphologies of PMMA/poly(styrene‐co‐acrylonitrile)/clay nanocomposites prepared by solution mixing

Nanocomposites of blends of PMMA and poly(styrene‐co‐acrylonitrile) (SAN) with natural (PM) or organically modified montmorillonite clays (Cloisite 30B, 25A, and 15A) were prepared by solution mixing and the effect of clay on the phase separation behavior along with morphologies of nanocomposites was investigated. Nanocomposites containing clay C30B prepared from methyl ethyl ketone showed the noticeable decrease in the cloud points. None of the other nanocomposites showed the increase in the cloud point. Location of clay particles in the phase separated matrix is observed to be different depending on the type of clays and solvents. The lowest cloud point of nanocomposites containing C30B may arise from the good dispersion of C30B where Clay C30B may act as the nucleating agent inducing phase separation. Dynamic mechanical and thermal analyses support above observations. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Conducting poly(styrene‐co‐divinylbenzene)/polypyrrole PolyHIPE composite foam prepared by chemical oxidative polymerization

Conducting poly(styrene‐co‐divinylbenzene)/polypyrrole (PPy) polyHIPE (polymerized high internal phase emulsion) composite foams were synthesized via chemical oxidative polymerization method. The effect of solvent and dopant type on the surface morphology and electrical conductivity of composite foams has been investigated. SEM micrographs showed that the morphology of PPy thin film on the internal surface of poly(styrene/divinylbenzene) (poly(St‐co‐DVB) polyHIPE support foam strongly depends on the solvent and dopant type used. Incorporation of dodecylbenzene solfunic acid‐sodium salt (DBSNa) as a dopant in chloroform solvent resulted in formation of a PPy thin film with higher molecular compact structure and electrical conductivity on the support foam as compared to other solvents and another dopant used. Fourier‐transform infrared spectroscopy was used to correlate the electrical conductivity of composite foams to their PPy structural parameters. As expected, the extended conjugation length of PPy in the presence of DBSNa dopant is the main reason for higher electrical conductivity of resultant composite foam. Electrical conductivity measurements revealed that the chemical aging of various conducting foams follows the first‐order kinetic model, which is a representative of a reaction‐controlled aging mechanism. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013