Comparison of characteristics of SAN–MMT nanocomposites prepared by emulsion and solution polymerization

Nonextractable styrene–acrylonitrile copolymer–montmollironite (SAN–MMT) nanocomposites were prepared by two different intercalation process: (1) a usual one‐step emulsion copolymerization in the presence of the Na⁺–MMT; and (2) a solution copolymerization with MMT modified by dimethyl dihydrogenated tallow ammonium. For comparative purposes, the copolymerization conditions (such as comonomer feed ratio and the polymerization temperature and times) were set up to be the same. The X‐ray diffraction pattern demonstrated that the net increase of basal spacing of the purified emulsion products (0.76 nm) far exceeded that of composite (0.39 nm) prepared by solution method. The average molecular masses recovered from the composite extracts revealed M_w = 53 × 10⁴ for emulsion products, while the composite made by solution yielded M_w = 4.8 × 10⁴ g/mol. Likewise, the hybrid from the emulsion polymerization exhibited higher stress at maximum load over the solution products. The dispersibility of MMT particles in the polymer matrix was investigated by using optical microscopy (OM) and scanning electron microscopy (SEM) for those unextracted samples. It was found that almost complete hybrids were obtained when the styrene (ST)–acrylonitryl (AN) comonomer was emulsion polymerized in the presence of Na⁺–MMT, yielding both better miscibility and intercalation capability. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2811–2819, 1999     

Polymerization kinetics and thermal properties of poly(alkyl methacrylate)/organomodified montmorillonite nanocomposites

The effect of the presence of organomodified nano‐montmorillonite (MMT) on the free radical polymerization kinetics of either ethyl methacrylate or butyl methacrylate was investigated. The in situ polymerization technique was selected with dispersion of the MMT nanoparticles into the corresponding monomer and subsequent bulk radical polymerization. Different types and amounts of MMT were used, including a sodium and several organomodified clays under the trade names Cloisite Na⁺ and Cloisite 15A, 25A and 30B. Reaction kinetics was measured gravimetrically and the nanocomposites formed were characterized with X‐ray diffraction (structure), gel permeation chromatography (molar mass distribution) and differential scanning calorimetry (glass transition temperature). Thermal degradation characteristics were measured with thermogravimetric analysis. Additional experiments with styrene as monomer were carried out in order to make clear the effect of the nanofiller on the polymerization kinetics. It was found that the presence of the bulk ammonium salt used as the organic modifier in MMT could influence the reaction kinetics when diffusion‐controlled phenomena occur. Reaction rate was slightly enhanced and nanocomposites with improved thermal stability were formed. In addition, the average molar mass and glass transition temperature of the polymer in the nanocomposites were slightly higher compared to the neat polymer. Copyright © 2012 Society of Chemical Industry     

One‐step synthesis of bis‐macromonomers of poly(1,3‐dioxolane) catalyzed by Maghnite‐H+

Telechelic poly(1,3‐dioxolane) (PDXL) bis‐macromonomers bearing methyl methacrylate end groups were prepared by cationic ring‐opening polymerization of 1,3‐dioxolane (DXL), in the presence of methacrylic anhydride, catalyzed by Maghnite‐H⁺ (Mag‐H⁺), in bulk and in solution. Maghnite is a montmorillonite sheet silicate clay, which exchanged with protons to produce Mag‐H⁺. The influence of the amount of Mag‐H⁺, monomer (DXL), and methacrylic anhydride on monomer conversion was studied. The polymerization yield and the molecular weight of α,ω‐bis‐unsaturated PDXLs prepared depend on the amount of Mag‐H⁺ used and the reaction time. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Complex formation of montmorillonite clay with polymers. Part 2: The use of montmorillonite clay–vinyl monomer complex as a comonomer in the copolymerization reaction of styrene–acrylonitrile monomers

The bulk copolymerization of styrene–acrylonitrile monomers using styrene‐N⁺–montmorillonite complex as a comonomer in the polymerization was studied. The X‐ray diffraction (XRD) analysis showed that part of the styrene‐N⁺–montmorillonite complex remained non‐dispersed (immiscible) and the copolymer was excluded from the interlayer of the immiscible part of the clay. The successive chemical extraction process revealed that a reasonable amount of the styrene–acrylonitrile copolymer was directly attached to the styrene‐N⁺–montmorillonite complex and enveloped the clay. Highly exfoliated clay lamella and nanospheres (3–5 nm) were observed by transmission electron microscopy (TEM). The montmorillonite clay assume two different morphologies, immiscible and exfoliated, on the basis of the XRD and TEM data. A simple method of calculation of the ratio of the exfoliated/immiscible amounts of the clay indicated that the amount of the styrene‐N⁺–montmorillonite complex exfoliated into separate lamella was 40 % (w/w) of the amount of the clay samples containing 2 % of the (styrene‐N⁺–montmorillonite complex) clay. This amount of exfoliated clay decreases with the increase of the concentration of the clay. The presence of the styrene‐N⁺–montmorillonite clay in the copolymerization reaction had a minor effect on both the copolymer composition and the molecular weight. Modification of the clay with the derivatized styrene monomer can achieve a nanocomposite using a percentage no more than 4 % (w/w) of complex in the copolymer. Copyright © 2004 Society of Chemical Industry     

Evaluation of polymethacrylic ionomer as compatibilizers for MCPA6/clay composites

The compatibilization effects provided by polymethacrylic ionomer (PMMA ionomer) on monomer‐casting polyamide6 (MCPA6)/clay (pristine sodium montmorillonite) composites were studied in this work. The PMMA ionomer used in this study was sodium polymethacrylate ionomer (PMMA Na⁺‐ionomer), which is a copolymer of methyl methacrylate and sodium methacrylate, prepared using emulsion polymerization. MCPA6/clay/PMMA Na⁺‐ionomer composites were prepared by in situ anionic ring‐opening polymerization (AROP) of ε‐caprolactam (CLA). X‐ray diffraction (XRD) and transmission electron microscopy (TEM) plus rheological measurement were used to characterize those composites. The results indicated that PMMA Na⁺‐ionomer is a good compatibilizer for this system. With increasing PMMA Na⁺‐ionomer content, a better dispersion of clay layers was successfully achieved in the MCPA6 matrix. Furthermore, differential scanning calorimetry (DSC) and XRD results indicated that well dispersed silicate layers limit the mobility of the MCPA6 molecule chains to crystallize, reduce the degree crystalline, and favor the formation of the γ‐crystalline form of the MCPA6 matrix. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Intercalated PS/Na+‐MMT Nanocomposites Prepared by Ultrasonically Initiated In Situ Emulsion Polymerization

Summary: A new technique, ultrasonically initiated in situ emulsion polymerization, was employed to prepare intercalated polystyrene/Na⁺‐MMT nanocomposites. FTIR, XRD, and TEM results confirm that the hydrophobic PS can easily intercalate into the galleries of hydrophilic montmorillonite via ultrasonically initiated in situ emulsion polymerization, taking advantages of the multi‐effects of ultrasonic irradiation, such as dispersion, pulverization, activation, and initiation. Properly reducing SDS concentration is beneficial to widen the d‐spacing between clay layers. However, the Na⁺‐MMT amount has little effect on the d‐spacing of nanocomposites. The glass transition temperature of nanocomposites increased as the percentage of clay increased, although the average molecular weight of PS decreased, and the decomposition temperature of the 1obtained nanocomposites moves to higher temperature.

TEM of PS/Na⁺‐MMT nanocomposite prepared by ultrasonically initiated in situ emulsion polymerization.     

Characterization of epoxy–clay hybrid composite prepared by emulsion polymerization

This article demonstrates the direct intercalation of an epoxy polymer in the interlayer of Na⁺–montmorillonite (MMT) by a step type of polymerization in an aqueous emulsion media. The synthesis and the results of structural and thermal characterizations for this hybrid composite are described. Equimolar quantities of bisphenol A and an epoxy prepolymer (n = 0.2) in an emulsion media were polymerized in the presence of Na⁺–MMT. X-ray diffraction (XRD) data obtained from the acetone-extracted products show that the basal spacing of the MMT is expanded from 0.96 to 1.64 nm. Thermal characterization for the postcured products by TGA and DSC gave evidence of enhanced thermal stabilities. SEM examination of the uncured products revealed that a disordered phase begins to appear with increasing polymer loading. However, the XRD profile supported that an overwhelming fraction of the nanocomposite contains intercalated clay. Also, the possibility of intercalation by the emulsion technique is proposed on the basis of the swelling characteristics of MMT in aqueous media and the sizes of micelles containing a monomer. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1997–2005, 1998     

Synthesis of Na+‐montmorillonite/amphiphilic polyurethane nanocomposite via bulk and coalescence emulsion polymerization

Polyurethane/clay nanocomposites have been synthesized using Na⁺‐montmorillonite (Na⁺‐MMT)/amphiphilic urethane precursor (APU) chains that have hydrophilic polyethylene oxide (PEO) chains and hydrophobic segments at the same molecules. Nanocomposites were synthesized through two different crosslinking polymerization methods. One is UV curing of melt mixed APU/Na⁺‐MMT mixtures; the other is coalescence polymerization of APU/Na⁺‐MMT emulsions. These two kinds of composites had intercalated silicate layers of Na⁺‐montmorillonite by insertion of PEO chains in APU chains, which was confirmed by X‐ray diffraction measurement and transmission electron microscopy. These composite films also showed improved mechanical properties compared to pristine APU films. Although the two kinds of nanocomposites exhibited the same degree of intercalation and were synthesized based on the same precursor chains, these nanocomposite films had the different mechanical properties. Nanocomposites synthesized using APU/Na⁺‐MMT emulsions, having microphase‐separated structure, had greater tensile strength than those prepared with melt‐mixed APU/Na⁺‐MMT mixtures. Location of intercalated Na⁺‐MMT by PEO chains at the oil–water interface also could be confirmed by rheological behavior of the APU/Na⁺‐MMT/water mixture. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3130–3136, 2003     

Intercalation of styrene–acrylonitrile copolymer in layered silicate by emulsion polymerization

A well‐defined styrene–acrylonitrile copolymer/montmorillonite (SAN‐MMT) nanocomposite has been prepared by emulsion copolymerization of styrene and acrylonitrile in the presence of sodium ion exchanged montmorillonite (Na⁺‐MMT). This direct and one‐step polymerization technique yielded nanocomposites intercalated with styrene‐acrylonitrile copolymer without occurrence of significant delamination of MMT. The purified products by hot tetrahydrofuran extraction for up to 5 days gave evidences of copolymer intercalation. Those infrared spectra obtained from the purified products revealed the characteristic absorbances due to styrene, acrylonitrile, and MMT. Room temperature powder X‐ray diffraction patterns of the purified product exhibited increased 001 d‐spacing about 1.60 nm. The transmission electron microscopy micrograph of unpurified products confirmed that the 1–2‐nm sized silicate layers are arranged in good order. The onset temperature of purified products are found to be moved to higher temperature, while the thermograms of differential scanning calorimetry show nothing observable transition. The modulus of elasticity of the product was increased with increasing content of MMT, whereas the stress at maximum load was decreased with the increments of MMT. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 179–188, 1999     

Composites of Semiaromatic Poly(Amide-Ester-Imide) Based on Bioactive Diacid and Oragnomodified Nanoclay Produced by Solution Intercalation Method: Thermal and Morphological Study

The aim of this work was to develop environmental friendly hydrophobic organomodified montmorillonite (OMMT) reinforced poly(amide-ester-imide) (PAEI) composites with enhanced their properties. At first, a chiral PAEI was obtained by step-growth polymerization of diol, N,N’-(1,3,5,7-tetraoxo-5,7-dihydropyrrolo[3,4-f]isoindole-2,6(1H,3H)-diyl)bis(4-hydroxybenzamide) with N-trimellitylimido-L-leucine. The blending of nanoclays with PAEI modifies the thermal property, and this change is strongly related to the dispersion of nanoclay in the polymer matrix. For this goal, positively charged chiral L-leucine was incorporated into the unmodified Cloisite-Na⁺ montmorillonite (MMT) for organomodification of MMT by cation-exchang method. Then PAEI/OMMT nanocomposites with different compositions were synthesized by solution intercalation method.     

Maghnite‐H+ as a cationic catalyst in the synthesis of poly(1,3‐dioxolane) and α,ω‐methacryloyloxy‐poly(1,3‐dioxolane)

The polymerization of 1,3‐dioxolane catalyzed by Maghnite‐H^+; (Mag‐H⁺), a montmorillonite sheet silicate clay exchanged with protons, was investigated. The cationic ring‐opening polymerization of 1,3‐dioxolane was initiated by Mag‐H⁺ at different temperatures (20, 30, 50, and 70°C) in bulk and in a solvent (dichloromethane). The effects of the amount of Mag‐H⁺ and the temperature were studied. The polymerization rate and the average molecular weights increased with an increase in the temperature and the proportion of the catalyst. These results indicated the cationic nature of the polymerization and suggested that the polymerization was initiated by proton addition to the monomer from Mag‐H⁺. Moreover, we used a simple method, in one step in bulk and in solution at room temperature (20°C), to prepare a telechelic bismacromonomer: α,ω‐bisunsaturated poly(1,3‐dioxolane). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 78–82, 2006     

Aqueous polymerization of protonated 4-vinylpyridine in montmorillonite

The polymerization of protonated 4-vinylpyridine (4-VPH⁺X⁻) in the interlayer zone of montmorillonite was studied. Polymerization is critically affected by the degree of surface coverage with a threshold value twice the cation exchange capacity of the mineral. Montmorillonite surfaces show selectivity for protonated 4-vinylpyridine favoring the formation of the quaternized form of the polyvinylpyridine polyelectrolyte. In situ polymerization of 4-VPH⁺X⁻ in the presence of 10 wt.% or lower sodium montmorillonite in aqueous solution yields exfoliated montmorillonite–polyelectrolyte heterostructures. The rate of polymerization in the presence of delaminated montmorillonite is much faster than in the absence. Mechanisms for intergallery and exogallery polymerization of 4-VPH⁺X⁻ are described.     

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     

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     

Electrical conductivity behavior of epoxy matrix nanocomposites with simultaneous dispersion of carbon nanotubes and clays

In this work, nanocomposites with simultaneous dispersion of multiwalled carbon nanotubes (MWCNT) and montmorillonite clays in an epoxy matrix were prepared by in situ polymerization. A high energy sonication was employed as the dispersion method, without the aid of solvents in the process. The simultaneous dispersion of clays with carbon nanotubes (CNT) in different polymeric matrices has shown a synergic potential of increasing mechanical properties and electrical conductivity. Two different montmorillonite clays were used: a natural (MMT‐Na⁺) and an organoclay (MMT‐30B). The nanocomposites had their electrical conductivity (σ) and dielectric constant (ε_r) measured by impedance spectroscopy. The sharp increase in electrical conductivity was found between 0.10 and 0.25 wt% of the MWCNTs. Transmission electron microscopy (TEM) of the samples showed a lower tendency of MWCNT segregation on the MMT‐30B clay surface, which is connected to intercalation/exfoliation in the matrix, that generates less free volume available for MWCNTs in the epoxy matrix. Data from electrical measurement showed that simultaneously adding organoclay reduces the electrical conduction in the nanocomposite. Moreover, conductivity and permittivity dispersion in low frequency suggest agglomeration of nanotubes surrounding the natural clay (MMT‐Na⁺) particles, which is confirmed by TEM. POLYM. COMPOS., 37:1603–1611, 2016. © 2014 Society of Plastics Engineers     

Properties of water‐soluble acrylic copolymer/montmorillonite nanocomposites for warp sizing

Acrylic copolymer/montmorillonite (MMT) nanocomposites for warp sizing were prepared in the presence of Na⁺‐MMT by the in situ intercalative polymerization of acrylic acid, acrylamide, and methyl acrylate in water solution. The properties of the solution and cast film were tested according to an application in sizing process of the nanocomposite size with various MMT contents. The results indicate that, for an exfoliated structure corresponding to the MMT content increasing to 7 wt %, the performance parameters of solution viscosity, glass‐transition temperature, and tensile strength of the film increased and the moisture sorption, abrasion loss, and elongation at break of the film decreased. When the intercalated structure of MMT was 9 wt %, the gathered MMT layers acted as a common inorganic filler in the copolymer matrix, with limited contribution to the properties of the composite. The adhesion work of the nanocomposite solution was calculated by use of the Young–Dupre relation, which showed maximum values at an MMT content of 3 wt % on the surfaces of both the polyester and cellulose films. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Morphological characterization and electrochemical/electrical properties of poly(N‐vinyl carbazole)/montmorillonite composites

A series of poly(N‐vinyl carbazole) (PNVCz)/sodium montmorillonite (Na⁺MMT) and PNVCz/organo‐MMT composite materials have been successfully prepared by in situ free radical polymerization with cerium ammonium nitrate (CAN) as initiator in the presence of inorganic nanolayers of hydrophilic Na⁺MMT or organophilic organo‐MMTs, modified with octadecylamine (ODA) and trimethyl stearyl ammonium (TMSA). The synthesized materials were subsequently characterized by Fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD), and differential scanning calorimetry (DSC). The distribution of MMT layers in the PNVCz matrix was also studied through polarized optical microscope (POM). Their electrochemical and electrical properties were investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The results showed that the type of intercalation agent and mixing method was affected on the structures and properties of composite materials. Both the interlayer spacing of clays and glass transition temperature of PNVCz was increased nearly from 1.18 nm to 3.53 nm and from 140°C to 185°, respectively. Their conductivities also increased relatively to that of the PNVCz homopolymer (10⁻¹¹–10⁻¹⁵ S/cm) and varied in the range of 10⁻¹⁰–10⁻⁵ S/cm, inversely dependent on the amount of MMT loading. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Preparation and characterization of transparent poly(methyl methacrylate)/Na+‐MMT nanocomposite films by solution casting

Films of poly(methyl methacrylate) (PMMA)/sodium montmorillonite (Na⁺‐MMT) nanocomposites have been successfully prepared utilizing Na⁺‐MMT by N,N‐dimethylformamide solution casting. The nanocomposite films show high transparency, enhanced thermal resistance, and mechanical properties in comparison with the neat polymer film. The transparency of the films was investigated by UV‐vis spectra. The exfoliated dispersion of Na⁺‐MMT platelets in nanocomposites were investigated by X‐ray diffraction and transmission electron microscopy. The enhanced thermal resistance and mechanical properties of PMMA were studied by thermal gravimetric analysis and dynamic mechanical analysis, respectively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and properties of polystyrene–clay nanocomposites via in situ intercalative polymerization

Organophilic montmorillonite (MMT) was prepared by ion exchange between Na⁺ ions in the clay and twin benzyldimethyloctadecylammonium bromine cations in an aqueous medium. The organophilic MMT particles were easily dispersed and swollen in styrene monomer. Polystyrene–MMT nanocomposites were prepared by the free‐radical polymerization of styrene containing dispersed clay. The intercalation spacing in the nanocomposites and the degree of dispersion of these composites were investigated with X‐ray diffraction and transmission electron microscopy, respectively. The nanocomposites had higher weight‐average molecular weights, lower glass‐transition temperatures, and better thermal stability (the decomposition temperature was improved by ca. 70°C) than the virgin polystyrene. The rheological behavior of the polystyrene–MMT nanocomposites was also studied. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 201–207, 2005     

Use of a new natural clay to produce poly(methyl methacrylate)‐based nanocomposites

Nanocomposites of poly(methyl methacrylate) (PMMA) filled with 3 wt% of modified natural Algerian clay (AC; montmorillonite type) were prepared by either in situ polymerization of methyl methacrylate initiated by 2,2′‐azobisisobutyronitrile or a melt‐mixing process with preformed PMMA via twin‐screw extrusion. The organo‐modification of the AC montmorillonite was achieved by ion exchange of Na⁺ with octadecyldimethylhydroxyethylammonium bromide. Up to now, this AC montmorillonite has found applications only in the petroleum industry as a rheological additive for drilling muds and in water purification processes; its use as reinforcement in polymer matrices has not been reported yet. The modified clay was characterized using X‐ray diffraction (XRD), which showed an important shift of the interlayer spacing after organo‐modification. The degree of dispersion of the clay in the polymer matrix and the resulting morphology of nanocomposites were evaluated using XRD and transmission electron microscopy. The resulting intercalated PMMA nanocomposites were analysed using thermogravimetric analysis and differential scanning calorimetry. The glass transition temperature of the nanocomposites was not significantly influenced by the presence of the modified clay while the thermal stability was considerably improved compared to unfilled PMMA. This Algerian natural montmorillonite can serve as reinforcing nanofiller for polymer matrices and is of real interest for the fabrication of nanocomposite materials with improved properties. Copyright © 2009 Society of Chemical Industry