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     

Catalytic activity of polymer–montmorillonite composites in chemical reactions

Polymer–clay composite material has been prepared by intercalation of polymeric ammonium salt onto the montmorillonite (Na–MMT) followed by grafted polymerization of hydroxyethyl methacrylate onto amine‐terminated poly(butadiene‐co‐acrylonitrile)–montmorillonite (ATBN–MMT) intercalate. The hydroxyl groups were modified to chloromethyl groups followed by conversion to onium salts, which are suitable as phase transfer catalysis. The catalytic activities of the supported catalysts were investigated in nucleophilic reactions of thiocyanate and cyanate ions with alkyl and aryl halides. The rates of the reactions have been investigated under different factors such as the nature and structure of the support, the amount of catalyst, the solvent, and the temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1121–1129, 2006     

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 (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     

Bulk polymerization of styrene in the presence of organomodified montmorillonite

The effect of montmorillonite (Cloisite 6A) on the bulk polymerization of styrene initiated by benzoyl peroxide (BPO) was studied by the dilatometric determination of the polymerization rates. The bulk polymerization rates increased as the montmorillonite input quantity increased. The effect became greater when the BPO concentration decreased. Under the assumption that clay participated in the radical initiation reaction of the chains, the reaction orders for clay and BPO were determined to be approximately 1.0 and 0.5, respectively. X‐ray diffraction and thermogravimetric analysis studies showed that the structure and properties of the obtained polystyrene (PS)/montmorillonite nanocomposites were greatly affected by the BPO concentration. With lower BPO concentrations, a larger interlayer distance and a higher extent of delamination for the clay were observed in the obtained PS/montmorillonite nanocomposites. The nanocomposites prepared with lower BPO concentrations also showed higher heat‐decomposition‐resistance temperatures. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1146–1152, 2005     

Electrolytic admicellar polymerization of pyrrole on natural rubber/clay nanocomposites

Organic–inorganic composites consisting of natural rubber (NR), polypyrrole (PPy), and sodium montmorillonite (Na‐MMT) were synthesized via electrolytic admicellar polymerization. A constant potential of 9 volts was chosen for the synthesis. The PPy concentration was fixed at 100 mM, and the clay contents were varied from 1 to 7 parts per hundred of rubber (phr). The synthesized nanocomposites were characterized by Fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD), scanning electron microscopy, and transmission electron microscopy (TEM), together with thermal stability (TGA), mechanical properties, and electrical conductivity (σ_dc) studies. The FTIR spectra indicated the characteristic peaks of both PPy and MMT clay and also evidenced a slight interaction between the PPy chain and the clay layers, verifying the success of electrolytic admicellar polymerization. XRD and TEM results pointed out the good dispersion of clay platelets in the polymer matrix, suggesting an exfoliated structure. The morphology of the nanocomposites was greatly dependent on the amount of MMT clay, especially at a 7 phr loading. The initial modulus and tensile strength of the nanocomposites containing the 7 phr loading were about four and two times higher, compared with unfilled NR/PPy, respectively. Thermal stability studies revealed a slight improvement in the decomposition temperature for the PPy component by the clay layers, whereas the opposite trend was found for the NR component. More interestingly, the electrical conductivity of the admicelled rubber increased significantly (～ 19–32 times) with increasing clay contents from 1 to 7 phr, in comparison with unfilled NR/PPy. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

Solid‐state graft polymerization of styrene in spherical polypropylene particles in the presence of montmorillonite

In this work, cetyltrimethyl ammonium bromide and methacryloyloxyethyhrimethyl ammonium chloride were used to prepare organophilic montmorillonite (O‐MMT). Then, polypropylene (PP)–clay nanocomposites were prepared by the in situ grafting polymerization of styrene (St)‐containing O‐MMT onto PP with tert‐butyl perbenzoate as an initiator in the solid state. Fourier transform infrared spectroscopy, gel permeation chromatography, transmission electron microscopy, and X‐ray diffraction were applied to study the structure of the layered silicate and modified PP. The surfaces of the composites and, thus, the distribution of the clay in the PP matrix were characterized by scanning electron microscopy. The rheology and mechanical properties were studied and are discussed. According to the characterization results, OMMT and St were already grafted onto the PP main chain. Also, the intercalated structure of montmorillonite could be stabilized, and a stable exfoliated structure could be attained. Namely, intercalated PP/OMMT nanocomposites were obtained. The rheological results clearly show that these PP/OMMT nanocomposites had long‐chain‐branched structures. The peroxide modification of PP had minor effects on the tensile and bending strengths of the modified PP; however, this modification resulted in a significant reduction in the impact strength. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of montmorillonite on the properties of thermosensitive poly(N‐isopropylacrylamide) composite hydrogels

Thermosensitive composite hydrogels containing various amounts of sodium montmorillonite (NaMM) and poly(N‐isopropylacrylamide) (pNIPAAm) were synthesized. Their equilibrium degree of swelling (DS) was measured in NaCl solutions of different ionic strength and at various temperatures. The DS decreased when increasing the clay content and no substantial shift in the phase transition temperature was noticed. The composite hydrogels investigated had a NaMM content ranging between 1.0 and 5.7 wt % (in 0.1M NaCl at 25°C). A considerable enhancement in the response to thermal stimuli was observed for NaMM contents >2–3 wt %. It is suggested that when the NaMM concentration approaches a critical value, the clay platelets can inhibit the formation of the hydrophobic skin layer that hinders shrinking in conventional pNIPAAm hydrogels. The effect of montmorillonite on the mechanical properties of the hydrogels was investigated by uniaxial compression tests, which showed that the modulus increases with the NaMM content. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1964–1971, 2004     

Properties of poly(ethylene terephthalate)–poly(ethylene naphthalene 2,6‐dicarboxylate) blends with montmorillonite clay

The production and properties of blends of poly(ethylene terephthalate) (PET) and poly(ethylene naphthalene 2,6‐dicarboxylate) (PEN) with three modified clays are reported. Octadecylammonium chloride and maleic anhydride (MAH) are used to modify the surface of the montmorillonite–Na⁺ clay particles (clay–Na⁺) to produce clay–C18 and clay–MAH, respectively, before they are mixed with the PET/PEN system. The transesterification degree, hydrophobicity and the effect of the clays on the mechanical, rheological and thermal properties are analysed. The PET–PEN/clay–C18 system does not show any improvements in the mechanical properties, which is attributed to poor exfoliation. On the other hand, in the PET–PEN/clay–MAH blends, the modified clay restricts crystallization of the matrix, as evidenced in the low value of the crystallization enthalpy. The process‐induced PET–PEN transesterification reaction is affected by the clay particles. Clay–C18 induces the largest proportion of naphthalate–ethylene–terephthalate (NET) blocks, as opposed to clay–Na⁺ which renders the lowest proportion. The clay readily incorporates in the bulk polymer, but receding contact‐angle measurements reveal a small influence of the particles on the surface properties of the sample. The clay–Na⁺ blend shows a predominant solid‐like behaviour, as evidenced by the magnitude of the storage modulus in the low‐frequency range, which reflects a high entanglement density and a substantial degree of polymer–particle interactions. Copyright © 2005 Society of Chemical Industry     

Effect of preshearing on the structure and properties of poly(methyl methacrylate)/clay nanocomposite panels

The effect of preshearing resin mixtures prior to casting on the structure and properties of in situ polymerized poly(methyl methacrylate)/clay nanocomposite panels was investigated. The preshearing was performed with a mechanical stirrer and controlled by varying mixing time. The structure, thermomechanical, and optical properties of the panels prepared with different preshearing times were analyzed by XRD, TEM, DMA, and UV/visible spectrophotometer. The properties of the panels increased with preshearing time because of improved intercalation and exfoliation of the clay. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Control of the anisotropic morphology of latex nanocomposites containing single montmorillonite clay particles prepared by conventional and reversible addition‐fragmentation chain transfer based emulsion polymerization

Single montmorillonite platelets have been successfully encapsulated by polymer through both a conventional and a reversible addition‐fragmentation chain transfer (RAFT) based emulsion polymerization. For both synthetic methods, the encapsulation process basically consisted of three steps: (i) adsorption of cationic RAFT copolymers (RAFT approach) or surfactant (conventional approach); (ii) high shear dispersion of the stabilized clay in aqueous solutions; (iii) starved‐feed addition of monomers starting the polymerization. In the conventional approach, the morphology of the latex/clay nanocomposites was close to the dumbbell shapes previously reported and did not depend on the presence of organic modifier as evidenced by cryotransmission electron microscopy and scanning electron microscopy. In the RAFT approach a completely different morphology was obtained which has been coined the cornflake morphology. With these two new approaches we can control the orientation of the clay platelets inside the latex particles which in turn can control the orientation of the clay platelets in a film. A perspective on possible applications of these different morphologies is given, e.g. their use in high barrier coatings. Copyright © 2012 Society of Chemical Industry     

Properties of poly(vinyl alcohol)—Bentonite clay nanocomposite films in relation to polymer–clay interactions

This study describes an effective way for the preparation of well‐dispersed, high‐loaded PVA/bentonite nanocomposites with improved properties, based on nanoscale interactions. To this end, a series of Poly(vinyl alcohol)—bentonite clay nanocomposites have been prepared via solvent casting technique and their properties were thoroughly investigated by atomic force microscopy, transmission electron microscopy, X‐Ray diffraction, oxygen and water permeability, water sorption along with mechanical and thermal studies. Microscopic and XRD techniques revealed highly organized regions. Clay content up to 10% led to nanocomposites with high degree of exfoliation. In addition samples with increased filler content (20%) demonstrated also, apart from the delaminated, well‐organized intercalated regions. The nanocomposites exhibited increased mechanical, thermal and gas barrier properties, though they retained their optical clarity. Thus, the Young's modulus of the sample containing 20% clay was increased by 193 times, while the oxygen permeability was decreased about seven times, in regard to the corresponding values of the neat polymer. The obtained results were explored on the basis of nanoscale phenomena and it was concluded that the organized structures and intercalated regions observed on highly loaded samples are attributed to the competitive effect between weaker polymer–polymer interactions in relation to stronger polymer–clay ones. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of intercalant content of mica on the various properties for the charged nanocomposite poly(N‐isopropyl acrylamide) hydrogels

In this study, we intend to adjust the charge properties of the poly(N‐isopropylacrylamide) [Poly(NIPAAm)] gel by using anionic clay and cationic monomer. Hence, two series of nanocomposite hydrogels bearing different charges were designed from NIPAAm, intercalated mica (IM) (NIM‐series) and NIPAAm, IM, trimethyl (acrylamido propyl) ammonium iodide (TMAAI) (NTIM‐series), respectively. The mica was first intercalated with different contents of intercalant, trimethyl (acrylamido propyl) ammonium chloride (TMAACl), based on the cationic exchange capacity (CEC) of mica. The effect of the CEC value of IM and IM content on the charge property, swelling behaviors, mechanical properties, and drug‐release behaviors of the present gels were investigated. Results showed that the negative charges for NIM series gels decrease with increase in CEC values of the IM (from ?11 to ?6 mV), the positive charges for NTIM series gels also decrease with increase in CEC values of the IM (from +36 to +18 mV). The swelling behaviors and mechanical properties for the NTIM gels were significantly enhanced by IM content and CEC values of the IM. The microstructures, morphologies, and drug‐release behaviors in these two series gels are also investigated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2277–2287, 2007     

Self‐assembled and crystallized composites made from poly(ether amine) and montmorillonite in the presence of copper(II) ions

Self‐assembled and crystallized composites made from montmorillonite (MMT) by intercalation with poly(ether amine) salts and copper(II) [Cu(II)] ions simultaneously were studied. The manipulation of the silicate unit structure of the secondary (001) lattice by physically imposed osmotic pressure on the platelet interlayer was used. Divalent copper salt assisted a strong depletion effect with balancing the counterions in the clay interlayer and resulted in the extension of the dimensions of the (001) plane by increasing the spacing expansion by more than two orders of magnitude. The simultaneous adsorption of Cu(II) and intercalation of poly(oxypropylene)amine (POP) salts onto the MMT units ultimately minimized their amorphous aggregation through electrostatic attraction between the negative surface and positive edge among the silicate units. Alternatively, the attraction force through face‐to‐face stacking on the silicate surface is proposed, and the conformation of the POP/Cu(II) complex aligned with the approaching platelets to form orderly structures. X‐ray diffraction of the MMT units exhibited a high order of reflection (i.e., (006)) in Bragg's pattern; this implied a repetitive regularity between the plate–plate distances. The high regularity disappeared when the Cu(II) adsorption exceeded the critical clay cation‐exchange capacity of 1.4. The conformation of the flexible polyether backbone was altered and could no longer sustain the plate distance and the symmetric packing was destroyed when the basal spacing was decreased from 82.6 to 18.0 Å. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of interfacial attraction on intercalation in polymer/clay nanocomposites

In order to examine the adhesive behavior of a polar polymer between hydrophilic clay layers, the so‐called glue effect, a clay intercalation by an ethylene–vinyl alcohol (EVOH) copolymer, which was capable of strong hydrogen bonding with the silicate surface of clay, was prepared by the melt intercalation technique and compared with a clay nanocomposite containing styrene–acrylonitrile (SAN) copolymer of less polar interaction energy in terms of the morphology and mechanical properties. Although initial penetration of the guest polymer into the gallery of the host clay occurred more rapidly for EVOH because of its strong hydrophilic nature, the dissociation of clay nanoplatelets was better developed for SAN with less polar interaction with clay, well evidencing the fact that the glue effect effectively affects the intercalation behavior of polymer/clay nanocomposites. However, the mechanical properties of the EVOH/clay nanocomposite were superior to those of SAN/clay nanocomposites. Although dissociation of respective silicate layers was poor for EVOH/clay nanocomposites, strong attractive energy stabilizes the interface between inorganic nanoparticles and the polymer matrix much more effectively, resulting in higher mechanical properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2749–2753, 2006     

Study of the biodegradable poly(ε‐caprolactone)/clay nanocomposite foams

In this article, biodegradable poly(ε‐caprolactone)/layered silicate nanocomposites were prepared and characterized. The dispersion state of modified clay in PCL matrix and its effect on thermal, rheological and mechanical properties of PCL were studied. The PCL/clay nanocomposites were then foamed using chemical foaming method. Cellular parameters such as mean cell size, cell wall thickness and cell densities of nanocomposite foams with different clay loading were collected. Effect of layered silicate on the structure and mechanical properties of PCL foams were evaluated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

DSC study of the cure kinetics during nanocomposite formation: Epoxy/poly(oxypropylene) diamine/organically modified montmorillonite system

The effect of an organically modified montmorillonite (OMMT) on the curing kinetics of a thermoset system based on a bisphenol A epoxy resin and a poly(oxypropylene)diamine curing agent were studied by means of differential scanning calorimetry (DSC) in isothermal and dynamic (constant heating rate) conditions. Montmorillonite and prepared composites were characterized by X‐ray diffraction analysis (XRD) and simultaneous differential scanning calorimetry–thermogravimetric analysis (DSC–TGA). Analysis of DSC data indicated that the presence of the filler has a very small effect on the kinetics of cure. A kinetic model, arising from an autocatalyzed reaction mechanism, was applied to the DSC data. Fairly good agreement between experimental and modeling data was obtained. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 550–557, 2006     

Preparation and properties of ethylene propylene rubber (EPR)–clay nanocomposites based on maleic anhydride‐modified EPR and organophilic clay

Ethylene propylene rubber–clay nanocomposites (EPR–CNs) were prepared by melt‐compounding maleic anhydride modified EPR (EPR‐MA) with organophilic clay, and their properties were examined. Silicate layers of organophilic clay were found to exfoliate and homogeneously disperse into the nanometer level in the nanocomposites by transmission electron microscopy observation. EPR–CNs exhibited higher tensile moduli compared to EPR‐MA and composites containing conventional fillers such as carbon black, talc. The storage moduli of EPR–CNs were also higher than those of EPR‐MA and the conventional composites. Creep resistances of EPR–CNs were much improved compared for EPR‐MA. Degree of swelling in hexadecane was remarkably restricted. Improvement of these properties is caused because dispersed silicate layers have much large interface with the EPR matrix and are thought to strongly restrain the EPR polymer chains. Nanocomposite technology using small amount of silicate layers is useful to improve properties of thermoplastic elastomer. Various kinds of thermoplastic elastomers are expected to be produced by loading of silicate layers with or without conventional fillers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 758–764, 2004     

Enhancement of corrosion protection effect of poly(styrene‐co‐acrylonitrile) by the incorporation of nanolayers of montmorillonite clay into copolymer matrix

A series of polymer–clay nanocomposite (PCN) materials that consisted of poly(styrene‐co‐acrylonitrile) (PSAN) and layered montmorillonite (MMT) clay were successfully prepared by effectively dispersing the inorganic nanolayers of MMT clay into the organic PSAN matrix by a conventional in situ thermal polymerization. First of all, organic styrene and AN monomers at a specific feeding ratio were simultaneously intercalated into the interlayer regions of organophilic clay hosts and followed by a typical free‐radical polymerization with benzyl peroxide as initiator. The as‐synthesized PCN materials were subsequently characterized by FTIR spectroscopy, wide‐angle powder X‐ray diffraction, and transmission electron microscopy. The as‐prepared PCN materials, in the form of coatings, incorporated with low clay loading (e.g., 1 wt %) on cold‐rolled steel, were found to be much superior in corrosion protection over those of bulk PSAN based on a series of standard electrochemical measurements of corrosion potential, polarization resistance, and corrosion current in 5 wt % aqueous NaCl electrolyte. Molecular weights of PSAN extracted from PCN materials and bulk PSAN were determined by gel permeation chromatography with THF as eluant. Effects of the material composition on the molecular barrier and thermal stability of PSAN along with PCN materials, in the form of both membrane and fine powder, were also studied by molecular permeability analysis, differential scanning calorimetry, and thermogravimetric analysis, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2269–2277, 2004