Effective enhancement of anticorrosive properties of polystyrene by polystyrene–clay nanocomposite materials

A series of polymer–clay nanocomposite (PCN) materials consisting of polystyrene (PS) and layered montmorillonite (MMT) clay was prepared by effectively dispersing the inorganic nanolayers of MMT clay in the organic PS matrix via in situ thermal polymerization. Organic styrene monomers were first intercalated into the interlayer regions of organophilic clay hosts, followed by a typical free radical polymerization with BPO as the initiator. The as‐synthesized PCN materials were characterized by infrared spectroscopy (IR), wide‐angle powder X‐ray diffraction (XRD) and transmission electron microscopy (TEM). PCN coatings with low clay loading (1 wt %) on cold‐rolled steel (CRS) were found to be superior in anticorrosion to those of bulk PS, based on a series of electrochemical measurements of corrosion potential, polarization resistance and corrosion current in a 5 wt % aqueous NaCl electrolyte. The molecular weights of PS extracted from PCN materials and bulk PS were determined by gel permeation chromatography (GPC) with tetrahydrofuran (THF) as the eluent. The effects of material composition on molecular barrier and thermal stability of PS and PCN materials, in the form of both free‐standing films and fine powders, were also studied by molecular permeability analysis, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1970–1976, 2004     

Enhanced corrosion protection coatings prepared from soluble electronically conductive polypyrrole‐clay nanocomposite materials

A series of electronically conductive nanocomposite materials that consisted of soluble polypyrrole (PPY) and layered montmorillonite (MMT) clay platelets were prepared by effectively dispersing the inorganic nanolayers of MMT clay in organic PPY matrix via an in situ oxidative polymerization with dodecylbenzene sulfonic acid (DBSA) as dopant. Organic pyrrole monomers were first intercalated into the interlayer regions of organophilic clay hosts and followed by a one‐step oxidative polymerization. The as‐synthesized electronically conductive polypyrrole–clay nanocomposite (PCN) materials were then characterized by Fourier transformation infrared (FTIR) spectroscopy, wide‐angle powder X‐ray diffraction (XRD), and transmission electron microscopy (TEM). PCNs in the form of coatings with low clay loading (e.g., 1.0 wt %) on cold‐rolled steel (CRS) were found to exhibit much better in corrosion protection over those of pristine PPY based on a series of electrochemical measurements including corrosion potential, polarization resistance, and corrosion current in 5 wt % aqueous NaCl electrolyte. Effects of the material composition on the thermal stability, optical properties, and electrical conductivity of pristine PPY along with PCN materials, in the form of fine powder, powder‐pressed pellet, and solution, were also studied by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), UV‐visible absorption spectra, and four‐point probe technique, respectively. The viscosity of PPY existed in PCN materials and pristine PPY were determined by viscometric analysis with m‐cresol as solvent. The heterogeneous nucleating effect of MMT clay platelets in PPY matrix was studied by wide‐angle powder XRD. The corresponding morphological images of the nucleating behavior of clay platelets in PPY matrix were investigated by scanning electron microscopy (SEM). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3264–3272, 2003     

Enhanced corrosion prevention effect of polysulfone–clay nanocomposite materials prepared by solution dispersion

A series of polymer–clay nanocomposite (PCN) materials containing polysulfone (PSF) and layered MMT clay were successfully prepared by effectively dispersing inorganic nanolayers of MMT clay in an organic PSF matrix via a solution dispersion technique. The synthesized PCN materials were subsequently investigated with a series of characterization techniques, including Fourier transform infrared (FTIR) spectroscopy, wide‐angle powder X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The prepared PCN coatings with low clay loading (1 wt %) on cold‐rolled steel (CRS) were found to be superior in corrosion prevention to those of bulk PSF, based on a series of electrochemical measurements of corrosion potential, polarization resistance, corrosion current and electrochemical impedance spectroscopy (EIS) in a 5 wt % aqueous NaCl electrolyte. The effects of material composition on the molecular barrier, mechanical strength and optical clarity of PSF and PCN materials, in the form of membranes, was also studied by molecular permeability analysis (GPA), dynamic mechanical analysis (DMA) and UV‐Visible transmission spectra, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 631–637, 2004     

Comparative studies of the properties of poly(methyl methacrylate)–clay nanocomposite materials prepared by in situ emulsion polymerization and solution dispersion

A series of polymer–clay nanocomposite (PCN) materials consisting of organic poly(methyl methacrylate) (PMMA) and inorganic montmorillonite (MMT) clay platelets were prepared successfully by the effective dispersion of nanolayers of the MMT clay in the PMMA framework through both in situ emulsion polymerization and solution dispersion. The as‐prepared PCN materials obtained with both approaches were subsequently characterized with wide‐angle powder X‐ray diffraction and transmission electron microscopy. For a comparison of the anticorrosion performance, a PCN material (e.g., 3 wt % clay loading) prepared by in situ emulsion polymerization, showing better dispersion of the clay platelets in the polymer matrix, exhibited better corrosion protection in the form of a coating on a cold‐rolled steel coupon than that prepared by solution dispersion, which showed a poor dispersion of the clay nanolayers according to a series of electrochemical corrosion measurements. Comparative studies of the optical clarity, molecular barrier properties, and thermal stability of samples prepared in both ways, as membranes and fine powders, were also performed with ultraviolet–visible transmission spectroscopy, molecular permeability analysis, thermogravimetric analysis, and differential scanning calorimetry. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1936–1946, 2004     

Preparation and properties of heterocyclically conjugated poly(3‐hexylthiophene)–clay nanocomposite materials

A series of heterocyclically conjugated polymer–clay nanocomposite (PCN) materials that consisted of organic poly(3‐hexylthiophene) (P3HT) and inorganic montmorillonite (MMT) clay platelets were prepared by in situ oxidative polymerization with FeCl₃ as an oxidant. The as‐synthesized PCN materials were characterized by Fourier transform infrared (FTIR) spectroscopy, wide‐angle powder X‐ray diffraction (WAXRD), and transmission electron microscopy (TEM). The effects of the material composition on the anticorrosion, gas barrier, thermal stability, flammability, mechanical strength, and electrical conductivity properties of the P3HT and PCN materials were studied by electrochemical corrosion measurements, gas‐permeability analysis (GPA), thermogrametric analysis (TGA), limiting oxygen index (LOI) measurements, dynamic mechanical analysis (DMA), and a four‐point probe technique, respectively. The molecular weights of extracted and bulk P3HT were determined by gel permeation chromatography (GPC) with THF as an eluant. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3438–3446, 2004     

Poly(N‐vinylcarbazole)–clay nanocomposite materials prepared by photoinitiated polymerization with triarylsulfonium salt initiator

A series of polymer–clay nanocomposite (PCN) materials that consist of poly(N‐vinylcarbazole) (PNVC) and layered montmorillonite (MMT) clay are prepared by effectively dispersing the inorganic nanolayers of MMT in an organic PNVC matrix via in situ photoinitiated polymerization with triarylsulfonium salt as the initiator. Organic NVC monomers are first intercalated into the interlayer regions of the organophilic clay hosts, followed by one‐step UV‐radiation polymerization. The as‐synthesized PCN materials are typically characterized by Fourier transform IR spectroscopy, wide‐angle X‐ray diffraction, and transmission electron microscopy. The molecular weights of PNVCs extracted from the PCN materials and the bulk PNVC are determined by gel permeation chromatography analysis with tetrahydrofuran as the eluant. The morphological image of the synthesized materials is observed by an optical polarizing microscope. The effects of the material composition on the optical properties and thermal stability of PNVCs and a series of PCN materials (solution and fine powder) are also studied by UV–visible absorption spectra measurements, thermogravimetric analysis, and differential scanning calorimetry, respectively. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1904–1912, 2004     

Effect of clay on the properties of poly(styrene‐co‐acrylonitrile)–clay nanocomposites

Clay‐dispersed poly(styrene‐co‐acrylonitrile) nanocomposites (PSAN) were synthesized by a free radical polymerization process. The montmorillonite (MMT) was modified by a cationic surfactant hexadecyltrimethylammonium chloride. The structures of PSAN were determined by wide‐angle X‐ray diffraction and FTIR spectroscopy. The dispersion of silicate layers in the polymer matrix was also revealed by transmission electron microscopy (TEM). It was confirmed that the clay was intercalated and exfoliated in the PSAN matrix. The increased thermal stability of PSAN with the addition of clay was observed by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The dielectric properties of PSAN were measured in the frequency range 100 Hz to 1 MHz at 35–70°C. It was found that the dielectric constant from the dipole orientation had been suppressed due to the intercalation of clay. The dielectric loss is strongly related to the residual sodium content of clay, which increases as the sodium content increases by the addition of clay. Copyright © 2004 Society of Chemical Industry     

Polyacrylamide–clay nanocomposite materials prepared by photopolymerization with acrylamide as an intercalating agent

A series of nanocomposite materials consisting of water‐soluble polyacrylamide (PAA) and layered montmorillonite (MMT) clay platelets were prepared by the effective dispersion of the inorganic nanolayers of the MMT clay in the organic PAA matrix via in situ ultraviolet‐radiation polymerization. The acrylamide monomers functioned as both the intercalating agent and the reacting monomers. As a representative procedure for the preparation of the nanocomposites, organic acrylamide monomers were first intercalated into the interlayer regions of acrylamide‐treated organophilic clay hosts, and this was followed by one‐step ultraviolet‐radiation free‐radical polymerization with benzil as a photoinitiator. The as‐prepared polyacrylamide–clay nanocomposite (PCN) materials were subsequently characterized by Fourier transform infrared spectroscopy, wide‐angle powder X‐ray diffraction, and transmission electron microscopy. The effects of the material composition on the thermal stability, optical clarity, and gas‐barrier properties of pristine PAA and PCN materials, in the forms of fine powders and membranes, were also studied by differential scanning calorimetry, thermogravimetric analysis, ultraviolet–visible transmission spectroscopy, and gas permeability analysis. The molecular weights of PAA extracted from PCN materials and pristine PAA were determined by gel permeation chromatography with tetrahydrofuran as an eluant. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3489–3496, 2004     

Preparation and properties of (BATB–ODPA) polyimide–clay nanocomposite materials

A series of polymer–clay nanocomposite (PCN) materials consisting of 1,4‐bis(4‐aminophenoxy)‐2‐tert‐butylbenzene–4,4′‐oxydiphthalic anhydride (BATB–ODPA) polyimide (PI) and layered montmorillonite (MMT) clay were successfully prepared by an in situ polymerization reaction through thermal imidization up to 300°C. The synthesized PCN materials were subsequently characterized by Fourier‐Transform infrared (FTIR) spectroscopy, wide‐angle powder X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The effects of material composition on thermal stability, mechanical strength, molecular permeability and optical clarity of bulk PI and PCN materials in the form of membranes were studied by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), molecular permeability analysis (GPA) and ultraviolet‐visible (UV/VIS) transmission spectra, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1072–1079, 2004     

Structure and properties of poly(o‐methoxyaniline)–clay nanocomposite materials

In this study, we prepared a series of polymer–clay nanocomposite (PCN) materials that consisted of an emeraldine base of poly(o‐methoxyaniline) and layered montmorillonite. Organic o‐methoxyaniline monomers were first intercalated into the interlayer regions of organophilic clay hosts followed by a one‐step in situ oxidative polymerization. The as‐synthesized PCN materials were subsequently characterized by FTIR spectroscopy, wide‐angle powder X‐ray diffraction, and transmission electron microscopy. The molecular weights of PMA extracted from PCN materials and bulk PMA were determined by GPC with THF as eluant. Effects of the material composition on the thermal stability, flame resistance, electrical conductivity, and corrosion inhibition performance of PMA, along with a series of PCN materials in the form of fine powder and coating, were also studied by TGA, limiting oxygen index measurements, four‐point probe technique, and electrochemical corrosion measurements, respectively. Morphological images of as‐synthesized materials were also investigated by SEM. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1072–1080, 2003     

Enhancement of corrosion protection effect of poly(o-ethoxyaniline) via the formation of poly(o-ethoxyaniline)-clay nanocomposite materials

A series of polymer-clay nanocomposite (PCN) materials that consisted of emeraldine base of poly(o-ethoxyaniline) (PEA) and layered montmorillonite (MMT) clay were prepared by effectively dispersing the inorganic MMT clay platelets in organic PEA matrix via in situ oxidative polymerization. Organic o-ethoxyaniline monomers were first intercalated into the interlayer regions of organophilic clay hosts and were followed by a one-step oxidative polymerization. The as-synthesized PCN materials were characterized by Fourier transform infrared (FTIR) spectroscopy, wide-angle X-ray diffraction (XRD) and transmission electron microscopy (TEM).PCN materials at low clay loading up to 3 wt% in the form of coating (e.g. 0.5 wt%) on cold-rolled steel (CRS) were found to exhibit much superior corrosion inhibition effect as compared to those of the bulk PEA by performing a series of electrochemical measurements of corrosion potential, polarization resistance, corrosion current and impedance spectroscopy in 5 wt% aqueous NaCl electrolyte. Furthermore, it was found that a further increase of clay loading up to 3 wt% results in a slightly enhanced molecular barrier property of PCN materials. The molecular weights of PEA extracted from PCN materials and bulk PEA were determined by gel permeation chromatography (GPC) analysis with NMP as eluant. Effects of the material composition on the molecular barrier, thermal stability, electrical conductivity and optical properties of PEA along with a series of PCN materials, in the form of free-standing film, fine powder and solution, were also studied by molecular permeability measurements (GPA), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), four-point probe technique and UV-vis spectra.     

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     

Synthesis and dielectric properties of poly(methyl methacrylate)–clay nanocomposite materials

Poly(methyl methacrylate) (PMMA)–clay nanocomposite (PCN) materials were synthesized through in situ intercalative polymerization. A cationic surfactant, [2(dimethylamino)ethyl]triphenylphosphonium bromide, was used as an intercalating agent with pristine Na⁺‐montmorillonite (MMT). The synthesized PCN materials were subsequently investigated by a series of characterization techniques, including wide‐angle powder X‐ray diffraction, Fourier transform IR spectroscopy, transmission electron microscopy, thermogravimetric analysis, and differential scanning calorimetry. Compared to pure PMMA, the PCN materials exhibit higher thermal degradation temperatures and glass‐transition temperatures. The dielectric properties of PCN blending with a commercial PMMA material in film form with clay loading from 0.5 to 5.0 wt % were measured under frequencies of 100 Hz–1 MHz at 35–100°C. Significantly depressed dielectric constants and losses were observed for these PCN‐blending materials. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2175–2181, 2005     

Preparation and properties of polyimide–clay nanocomposite materials for anticorrosion application

A series of polymer–clay nanocomposite (PCN) materials that consist of organosoluble polyimide and layered montmorillonite clay were prepared by the solution dispersion technique. The organosoluble polyimide containing non‐coplanar moiety in diamine monomer and flexible bridging linkages in dianhydride monomer was synthesized by chemical imidization. The as‐synthesized PCN materials were characterized by infrared spectroscopy, wide‐angle powder X‐ray diffraction, and transmission electron microscopy. The organosoluble polyimide showed better corrosion resistance compared to polyaniline, poly(o‐ethoxyaniline) and poly(methyl methacrylate) by using a series of standard electrochemical corrosion measurements of corrosion potential, polarization resistance, and corrosion current in 5 wt % aqueous NaCl electrolyte. Polyimide–clay nanocomposite materials incorporated with low loading of clay were found to further improve corrosion inhibition over pure polyimide. Effects of the material composition on the O₂/H₂O molecular permeability, optical clarity, and thermal properties of polyimide–clay nanocomposite materials were studied by molecular permeability analysis, UV–visible transmission spectra, thermogravimetric analysis, and differential scanning calorimetry, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3573–3582, 2004     

Synthesis and dielectric properties of polystyrene‐clay nanocomposite materials

Polystyrene‐clay nanocomposite (PsCN) materials were synthesized and their properties of crystallinity, thermal behavior, and dielectric characteristics were investigated. A polymerizable cationic surfactant, [2‐(dimethylamino)ethyl]triphenylphonium bromide, was used for the intercalation of montmorillonite (MMT). The organophilic MMT was prepared by Na⁺‐exchanged MMT and ammonium cations of a cationic surfactant in an aqueous medium. Organophilic styrene monomers were intercalated into the interlayer regions of organophilic clay hosts followed by a free‐radical polymerization. Exfoliation to 2 wt % MMT in the polystyrene (PS) matrix was achieved as revealed by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Thermal properties by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were also studied. The dielectric properties of PsCNs in the form of film with clay loading from 1.0 to 5.0 wt % were measured under frequencies of 100 Hz–1 MHz at 25–70°C. A decreased dielectric constant and low dielectric loss were observed for PsCN materials. The dielectric response at low frequency that originated from dipole orientation was suppressed due to the intercalation of clay materials. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1368–1373, 2004     

High‐performance polyimide–clay nanocomposite materials based on a dual intercalating agent system

BACKGROUND: Polymer–clay nanocomposites (PCNs) have attracted considerable interest in recent years owing to their unique physical and chemical properties that lead to a wide range of applications. A series of PCN materials consisting of polyimide and layered montmorillonite (MMT) clay were successfully prepared by in situ polymerization. RESULTS: Silicate layers are better dispersed in polymer matrices when dual intercalating agents (hexadecyltrimethylammonium bromide–4,4′‐oxydianiline) are applied for MMT modification according to wide‐angle X‐ray diffraction and transmission electron microscopy studies. Effects of single and dual intercalating agents on thermal stability, mechanical strength and the molecular barrier of PCN materials consisting of organo‐modified MMT were studied by means of thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analyses, gas permeability analysis and vapor permeability analysis. CONCLUSION: Improved thermal and mechanical stabilities, as well as barrier properties were observed for the PCN materials containing dual intercalating agent‐modified MMT. Copyright © 2008 Society of Chemical Industry     

Studies on heterogeneous nucleation effect of dispersing intercalated montmorillonite clay platelets in polyaniline matrix

In this article, a series of nanocomposite materials that consisted of emeraldine base (EB) of polyaniline (PANI) and montmorillonite (MMT) clay were prepared by effectively dispersing the inorganic MMT clay platelets into organic PANI matrix via in situ chemically oxidative polymerization. Organic aniline monomers were first intercalated into the interlayer regions of organophilic clay hosts and followed by an one‐step oxidative polymerization with ammonium persulfate as oxidant. The as‐synthesized PANI‐clay nanocomposite (PCN) materials were characterized by Fourier‐Transformation infrared spectroscopy and transmission electron microscopy. It should be noted that the EB of PANI in the presence of dispersed intercalated MMT clay platelets was found to display an observable enhancement in polymer crystallinity as compared with that of neat PANI based on series of investigations of wide‐angle powder X‐ray diffraction patterns and differential scanning calorimetric studies. This remarkable increase of polymer crystallinity might be resulted from the effective heterogeneous nucleation effect of dispersed clay platelets existed in PCN materials. The surface morphology study of PCN materials was further evaluated by polarizing optical microscopy, scanning electron microscopy, and atomic force microscopy. POLYM. COMPOS., 31:2049–2056, 2010. © 2010 Society of Plastics Engineers     

Preparation of exfoliated high‐impact polystyrene/MMT nanocomposites via in situ polymerization under controlling viscosity of the reaction medium

Exfoliated high‐impact polystyrene (HIPS)/montmorillonite (MMT) nanocomposites were prepared via in situ polymerization of styrene in the presence of polybutadiene, using an intercalated cationic radical initiator‐MMT hybrid (organoclay). In the solution polymerization in toluene, the silicate layers of the clay were well exfoliated, due to the low extra‐gallery viscosity that can facilitate the diffusion of styrene monomers into the clay layers during the polymerization. The exfoliated HIPS/MMT nanocomposites were also successfully prepared by controlling the viscosity of the reaction medium with prolong swelling of the organoclay in styrene, prior to bulk polymerization. The HIPS/MMT nanocomposites, obtained from bulk polymerization, exhibited a significant improvement in thermal stability, compared to those obtained from solution polymerization as well as the pure polymer counterparts. POLYM. COMPOS., 2008. © 2007 Society of Plastics Engineers     

Preparation and properties of poly(vinyl alcohol)-clay nanocomposite materials

A series of polymer-clay nanocomposite (PCN) materials that consist of poly(vinyl alcohol) (PVA) and layered montmorillonite (MMT) clay are prepared by effectively dispersing the inorganic nanolayers of MMT clay in organic PVA matrix via an in situ free radical polymerization with AIBN as initiator. Organic vinyl acetate monomers are first intercalated into the interlayer regions of organophilic clay hosts and followed by a one-step free radical polymerization. The prepared poly(vinyl acetate)-clay (PVAc-clay) solution are then saponified via direct-hydrolysis with NaOH solution to form PVA-clay nanocomposite materials. The as-synthesized PCN materials are typically characterized by Fourier-Transformation infrared (FTIR) spectroscopy, wide-angle X-ray diffraction and transmission electron microscopy.The molecular weights of poly(vinyl alcohol) (PVA) extracted from polymer-clay nanocomposite (PCN) materials and bulk PVA are determined by gel permeation chromatography (GPC) analysis with THF as eluant. The viscosity property of PCN materials with different feeding amount of MMT clay is studied by an ubbelohode capillary viscometer. The morphological image of as-synthesized materials is studied by scanning electron microscopy (SEM) and optical polarizing microscope (OPM). Effects of the material composition on the thermal stability, mechanical strength, optical clarity of PVA along with a series of PCN materials, in the form of fine powder and free-standing film, are also studied by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analyzer (DMA) and UV-visible transmission spectra, respectively.     

Polystyrene nanocomposite materials by in situ polymerization into montmorillonite–vinyl monomer interlayers

A different series of new polystyrene–clay nanocomposites have been prepared by grafting polymerization of styrene with vinyl‐montmorillonite (MMT) clay. The synthesis was achieved through two steps. The first step is the modification of clay with the vinyl monomers, such as N,N‐dimethyl‐n‐octadecyl‐4‐vinylbenzyl‐ammonium chloride, n‐octadecyl‐4‐vinylbenzyl‐ammonium chloride, triphenyl‐4‐vinylbenzyl‐phosphonium chloride, and tri‐n‐butyl‐4‐vinylbenzyl‐phosphonium chloride. The second step is the polymerization of styrene with different ratios of vinyl‐MMT clay. The materials produced were characterized by different physical and chemical methods: (1) IR spectra, confirming the intercalation of the vinyl‐cation within the clay interlayers; (2) thermogravimetric analysis (TGA), showing higher thermal stability for PS–nanocomposites than polystyrene (PS) and higher thermal stability of nanocomposites with of phosphonium moieties than nanocomposites with ammonium moieties; (3) swelling measurements in different organic solvents, showing that the swelling degree in hydrophobic solvents increases as the clay ratio decreases; (4) X‐ray diffraction (XRD), illustrating that the nanocomposites were exfoliated at up to a 25 wt % of organoclay content; and (5) scanning electron microscopy (SEM), showing a complete dispersion of PS into clay galleries. Also, transmission electron microscopy (TEM) showed nanosize spherical particles of ～ 150–400 nm appearing in the images. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3739–3750, 2007