Exfoliated poly(methyl methacrylate) and polystyrene nanocomposites occur when the clay cation contains a vinyl monomer

The bulk polymerization of methyl methacrylate and styrene in the presence of an organically modified clay containing a vinyl group that can be involved in the polymerization produces exfoliated nanocomposites. These nanocomposites have been characterized by X‐ray diffraction, transmission electron microscopy, thermogravimetric analysis, mechanical properties, and cone calorimetry. The onset temperature of thermal degradation increases with the mechanical properties. The peak heat release rate is significantly reduced for nanocomposites containing 3 or 5% clay. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1124–1135, 2003     

Poly(1‐butene)/clay nanocomposites: Preparation and properties

The preparation and properties of poly(1‐butene) (PB)/clay nanocomposites are described for the first time. Nanocomposites were prepared with the melt‐intercalation technique, using organically modified clay. The X‐ray diffraction patterns portrayed well‐defined diffraction peaks at higher d‐spacing than pristine clay, confirming the intercalation of polymer in silicate layers. Because PB exhibits time‐dependent polymorphism, the effect of clay on the phase transformation of PB was examined with thermal analysis. The phase transformation from a metastable tetragonal form to a stable hexagonal form was enhanced because of incorporation of layered silicates in the polymer matrix. The nanocomposites exhibited about a 40–140% increase in storage modulus depending on the clay content and significantly lower coefficient of thermal expansion. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1014–1021, 2003     

Effect of Organic Nano Carboncapsule Incorporated Modified Clay on Fire‐Retardancy of PMMA Nanocomposites

Here we investigate a new type of highly flame retardant poly(methyl methacrylate) (PMMA) nanocomposite by bulk polymerization of methyl methacrylate (MMA) in the presence of organic nano carboncapsule (OCNC/NCNC)‐incorporated modified montmorillonites (CL120, CL42). The morphology of the modified clay was confirmed by X‐ray diffraction (XRD), and Fourier transform infrared (FT‐IR) spectroscopy was used to identify the functional groups in the clay. The nano morphological characterization of the clay in the PMMA matrix was confirmed by XRD and transmission electron microscopy (TEM). The thermal and mechanical properties of the PMMA nanocomposites were investigated by thermogravimetry and dynamic mechanical analysis, respectively. PMMA containing organo nano carboncapsule‐doped CL42 modified cocoamphodipropionate (K2) (P‐O‐CL42) could achieve very high thermal stability compared to pristine PMMA. The 5% thermal decomposition temperature (T _5d) increased by 63.2°C. Storage modulus of PMMA nanocomposites measured by DMA analysis. An enhancement of storage modulus and significant reduction in the peak heat release (PHR) rate were observed in the almost all PMMA nanocomposites as compared to pristine PMMA. Moreover, these results suggest that PMMA nanocomposites can have potential applications in the building industry and the medical field.     

Silicon‐methoxide‐modified clays and their polystyrene nanocomposites

Silicon‐methoxide‐containing modified clays were obtained through cationic exchange between the sodium clay and the ammonium cation of [3‐(trimethoxysilyl)propyl]octadecyldimethylammonium chloride (Si18). The nanocomposites were prepared through bulk polymerization of styrene in which the Si18 clay was dispersed. The silicon‐methoxide offers the possibility of reaction between the methoxide and a clay hydroxyl group to link together the cation and the clay. The nanocomposites were characterized by X‐ray diffraction, transmission electron microscopy, and atomic force microscopy. Their thermal stability and flame retardancy were measured by thermogravimetric analysis (TGA) and cone calorimetry. Linkage between the silicon and the clay apparently occurs in the clay but is not likely to occur in the nanocomposite, perhaps because of the presence of the polystyrene spreading the distance between the reactive sites, which makes reaction more difficult. The results from TGA and cone calorimetry were similar to those obtained with other nanocomposites. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1498–1503, 2002     

Brominated poly(isobutylene‐co‐para‐methylstyrene) (BIMS)‐clay nanocomposites: Synthesis and characterization

In this work, preparation and properties of different nanoclays modified by organic amines (octadecyl amine, a primary amine, and hexadecyltrimethylammonium bromide, a tertiary amine) and brominated polyisobutylene‐co‐paramethylstyrene (BIMS)‐clay nanocomposites are reported. The clays and the rubber nanocomposites have been characterized with the help of Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), and X‐ray diffraction (XRD). The X‐ray diffraction peaks observed in the range of 3 °–10 ° for the modified clays disappear in the rubber nanocomposites. TEM photographs show predominantly exfoliation of the clays in the range of 12 ± 4 nm in the BIMS. In the FTIR spectra of the nanocomposites, there are common peaks of virgin rubber as well as those of the clays. Excellent improvement in mechanical properties like tensile strength, elongation at break, and modulus is observed on incorporation of the nanoclays in the BIMS. Structure‐property correlation in the above nanocomposites is attempted. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4489–4502, 2004     

Phase behavior of modified montmorillonite– poly(ϵ‐caprolactone) nanocomposites

The thermal behavior and overall isothermal crystallization kinetics of a series of organophilic modified montmorillonite–poly(?‐caprolactone) nanocomposites were investigated. In general, the thermal behavior was influenced more by the type of dispersion than by the clay content. For nanocomposites in which silicate platelets were predominantly dispersed in the polymer matrix to give exfoliated structures, the thermal properties were improved with respect to those of neat poly(?‐caprolactone), whereas in those cases in which simply intercalated structures were attained, the thermal properties regularly decayed as the clay content increased. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1321–1332, 2004     

Preparation and characterization of melt‐compounded polyethylene/vermiculite nanocomposites

Polyethylene (PE)‐layered vermiculite (VMT) nanocomposites were fabricated via direct melt compounding in a twin‐screw extruder followed by injection molding. Exfoliated PE/VMT nanocomposites were readily prepared via in situ melt mixing of maleic anhydride modified VMT with PE. Maleic anhydride acts as either the intercalation agent for VMT or as a compatibilizer for the PE and VMT phases. X‐ray diffraction and transmission electron microscopic observations revealed the formation of exfoliated PE/VMT nanocomposites. The experimental results showed that the storage modulus and strength of nanocomposites tend to increase with an increasing VMT content. Nearly 25.35% increment in the tensile strength and 50% increment in the storage modulus were achieved by incorporating 4 wt % VMT into PE. The thermal properties of the nanocomposites were investigated by dynamic mechanical analysis and differential scanning calorimetry. The glass‐transition temperature of PE/VMT nanocomposites appeared to increase upon the introduction of VMT into the PE matrix. The effects of maleic anhydride addition on the formation of the PE/VMT nanocomposites are discussed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1476–1484, 2003     

Synthesis,rheology, and morphology of nylon‐11/layered silicate nanocomposite

Exfoliated nylon‐11/layered silicate nanocomposites were prepared via in situ polymerization by dispersing organoclay in 11‐aminoundecanoic acid monomer. The original clay was modified by a novel method with 11‐aminoundecanoic acid. In situ Fourier transform infrared spectroscopy results show that stronger hydrogen bonds exist between nylon‐11 and organoclay than that of between nylon‐11 and original clay. The linear dynamic viscoelasticity of organoclay nanocomposites was investigated. Before taking rheological measurements, the exfoliated and intercalating structures and the thermal properties were characterized using X‐ray diffraction, transmission electron microscopy, differential scanning calorimetry, and thermogravimetric analysis. The results show that the clay was uniformly distributed in nylon‐11 matrix during in situ polymerization of clay with 4 wt % or less. The presence of clay in nylon‐11 matrix increased the crystallization temperature and the thermal stability of nanocomposites prepared. Rheological properties such as storage modulus, loss modulus, and relative viscosity have close relationship with the dispersion favorably compatible with the organically modified clay. Comparing with neat nylon‐11, the nanocomposites show much higher dynamic modulus and stronger shear thinning behavior. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2161–2172, 2006     

Effect of a silicate filler on the crystal morphology of poly(trimethylene terephthalate)/clay nanocomposites

A series of intercalated poly(trimethylene terephthalate) (PTT)/clay nanocomposites were prepared in a twin‐screw extruder by the melt mixing of PTT with either quaternary or ternary ammonium salt‐modified clays. The morphology and structure, along with the crystallization and melting behavior, and the dynamic mechanical behavior of the composites were characterized by X‐ray diffraction, transmission electron microscopy, differential scanning calorimetry, and dynamic mechanical thermal analysis. The results showed that the PTT chains could undergo center‐mass transport from the polymer melt into the silicate galleries successfully during the blending and extrusion process. More coherent stacking of the silicate layers was reserved at higher clay concentrations and shorter blend times. Compared with conventionally compounded composites, the nanoscale‐dispersed organophilic clays were more effective as crystal nucleation agents. The influence of the nanosilicates on the crystallization and melting behavior of PTT became distinct when the concentration of clay was around 3 wt %. The changes in the crystallization behavior of the polymer/clay nanocomposites depended not only on the size of the silicates but also on the intrinsic crystallization characteristics of the polymers. The resulting nanocomposites showed an increase in the dynamic modulus of PTT and a decrease in the relaxation intensity (both in loss modulus and loss tangent magnitude). © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2275–2289, 2003     

Influence of Fe‐MMT on crosslinking and thermal degradation in silicone rubber/clay nanocomposites

In this article, silicone rubber (SR)/clay nanocomposites were synthesized by a melt‐intercalation process using synthetic Fe‐montmorillonite (Fe‐MMT) and natural Na‐MMT which were modified by cetyltrimethyl ammonium bromide (CTAB). This study has been designed to determine if the presence of structural iron in the matrix can result in radical trapping and then enhance thermal stability, affect the crosslinking degree and elongation. The SR/clay nanocomposites were characterized by X‐ray diffraction (XRD) patterns and transmission electron microscopy (TEM). Exfoliated and intercalated nanocomposites were obtained. Thermo gravimetric analysis (TGA) and mechanical performance were applied to test the properties of the SR/clay nanocomposites. The presence of iron significantly increased the onset temperature of thermal degradation in SR/Fe‐MMT nanocomposites. The thermal stability, gel fraction and mechanical property of SR/Fe‐MMT were different from the SR/Na‐MMT nanocomposites. So the iron not only in thermal degradation but in the vulcanization process acted as an antioxidant and radicals trap. Copyright © 2006 John Wiley & Sons, Ltd.     

Grafting of polymers onto and/or from silica surface during the polymerization of vinyl monomers in the presence of γ‐ray‐irradiated silica

The effects of radicals on silica surface, which were formed by γ‐ray irradiation, on the polymerization of vinyl monomers were investigated. It was found that the polymerization of styrene was remarkably retarded in the presence of γ‐ray‐irradiated silica above 60 °C, at which thermal polymerization of styrene is readily initiated. During the polymerization, a part of polystyrene formed was grafted onto the silica surface but percentage of grafting was very small. On the other hand, no retardation of the polymerization of styrene was observed in the presence of γ‐ray‐irradiated silica below 50 °C; the polymerization tends to accelerate and polystyrene was grafted onto the silica surface. Poly(vinyl acetate) and poly(methyl methacrylate) (MMA) were also grafted onto the surface during the polymerization in the presence of γ‐ray‐irradiated silica. The grafting of polymers onto the silica surface was confirmed by thermal decomposition GC‐MS. It was considered that at lower temperature, the grafting based on the propagation of polystyrene from surface radical (“grafting from” mechanism) preferentially proceeded. On the contrary, at higher temperature, the coupling reaction of propagating polymer radicals with surface radicals (“grafting onto” mechanism) proceeded to give relatively higher molecular weight polymer‐grafted silica. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2972–2979, 2006     

ATRP of MMA under 60Co γ‐irradiation at room temperature

In this work, atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) was successfully carried out at room temperature (25 °C) under ⁶⁰Co γ‐irradiation environment. The polymerization proceeded smoothly with high conversion (>90%) within 7 h. The polymerizations kept the features of controlled radical polymerization: first‐order kinetics, well‐predetermined number‐average molecular weights (M_n,GPC), and narrow molecular weight distributions (M_w/M_n < 1.25). ¹H NMR spectroscope and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry confirmed that poly(methyl methacrylate) (PMMA) chain was end‐capped by the initiator moieties. The Cu(II) concentration could reduce to 20 ppm level while keeping good control over molecular weights. This is the first successful example for the ATRP of MMA under ⁶⁰Co γ‐irradiation at room temperature. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Physicochemical characterization of α‐chitin, β‐chitin,and γ‐chitin separated from natural resources

We isolated α‐chitin, β‐chitin, and γ‐chitin from natural resources by a chemical method to investigate the crystalline structure of chitin. Its characteristics were identified with Fourier transform infrared (FTIR) and solid‐state cross‐polarization/magic‐angle‐spinning (CP–MAS) ¹³C NMR spectrophotometers. The average molecular weights of α‐chitin, β‐chitin, and γ‐chitin, calculated with the relative viscosity, were about 701, 612, and 524 kDa, respectively. In the FTIR spectra, α‐chitin, β‐chitin, and γ‐chitin showed a doublet, a singlet, and a semidoublet at the amide I band, respectively. The solid‐state CP–MAS ¹³C NMR spectra revealed that α‐chitin was sharply resolved around 73 and 75 ppm and that β‐chitin had a singlet around 74 ppm. For γ‐chitin, two signals appeared around 73 and 75 ppm. From the X‐ray diffraction results, α‐chitin was observed to have four crystalline reflections at 9.6, 19.6, 21.1, and 23.7 by the crystalline structure. Also, β‐chitin was observed to have two crystalline reflections at 9.1 and 20.3 by the crystalline structure. γ‐Chitin, having an antiparallel and parallel structure, was similar in its X‐ray diffraction patterns to α‐chitin. The exothermic peaks of α‐chitin, β‐chitin, and γ‐chitin appeared at 330, 230, and 310, respectively. The thermal decomposition activation energies of α‐chitin, β‐chitin, and γ‐chitin, calculated by thermogravimetric analysis, were 60.56, 58.16, and 59.26 kJ mol^?1, respectively. With the Arrhenius law, ln β was plotted against the reciprocal of the maximum decomposition temperature as a straight line; there was a large slope for large activation energies and a small slope for small activation energies. α‐Chitin with high activation energies was very temperature‐sensitive; β‐Chitin with low activation energies was relatively temperature‐insensitive. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3423–3432, 2004     

Controlled/living free‐radical copolymerization of 4‐(azidocarbonyl) phenyl methacrylate with methyl acrylate under 60Co γ‐ray irradiation

A new vinyl acyl azide monomer, 4‐(azidocarbonyl) phenyl methacrylate, has been synthesized and characterized by NMR and FTIR spectroscopy. The thermal stability of the new monomer has been investigated with FTIR and thermal gravimetry/differential thermal analysis (TG/DTA), and the monomer has been demonstrated to be stable below 50 °C in the solid state. The copolymerizations of the new monomer with methyl acrylate have been carried out at room temperature under ⁶⁰Co γ‐ray irradiation in the presence of benzyl 1H‐imidazole‐1‐carbodithioate. The results show that the polymerizations bear all the characteristics of controlled/living free‐radical polymerizations, such as the molecular weight increasing linearly with the monomer conversion, the molecular weight distribution being narrow (<1.20), and a linear relationship existing between ln([M]₀/[M]) and the polymerization time. The data from ¹H NMR and FTIR confirm that no change in the acyl azide groups has occurred in the polymerization process and that acyl azide copolymers have been obtained. The thermal stability of the polymers has also been investigated with TG/DTA and FTIR. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2609–2616, 2007     

Grafting of montmorillonite nano‐clay with butyl acrylate and methyl methacrylate by atom transfer radical polymerization: Blends with poly(BuA‐co‐MMA)

11‐(2‐Bromo‐2‐methyl)propionyl‐oxy‐undecyl trichlorosilane atom transfer radical polymerization (ATRP) initiator was covalently attached on montmorillonite clay platelets via silylation reactions. The initiator clay was used to polymerize butyl acrylate (BuA) and methyl methacrylate (MMA) on the clay surface. Polymerization was performed in bulk monomer solution or in DMSO. Polymer modified clay was mixed with a poly(BuA‐co‐MMA) matrix. Small angle X‐ray scattering (SAXS) and transmission electron microscopy (TEM) showed that clay modified in DMSO gave exfoliated composites when mixed with the matrix copolymer. Mechanical properties of the composites were studied by dynamic mechanical thermal analysis (DMTA). The results showed that the mechanical properties were improved as a function of clay content, as well with an increasing homogeneity of the nanocomposite. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3086–3097, 2009     

Effect of polymerically‐modified clay structure on the morphology and properties of UV‐cured polyurethane acrylate/clay nanocomposites

Polyurethane acrylate (PUA)/clay nanocomposites were prepared by UV‐curing from a series of styrene‐based polymerically‐modified clays and PUA resin. Effect of the chemical structure of the polymeric surfactants on the morphology and tensile properties of nanocomposites has been explored. X‐ray diffraction (XRD) and transmission electron microscopy (TEM) experimental results indicated that surfactants having hydroxyl or amino groups show better dispersion and some of the clay platelets were fully exfoliated. However, the composites formed from pristine clay and other polymerically‐modified clays without hydroxyl or amino groups typically contained both tactoids and intercalated structure. The mechanical properties of PUA composites were greatly improved where the organoclays dispersed well. Thermogravimetric analysis (TGA) and differential scanning calorimeter (DSC) were carried out to examine the thermal properties of the composites. The results showed that the loading of polymerically‐modified clays do not effect the thermal stability, but increased the Tgs of PUA/clay composites. Copyright © 2010 John Wiley & Sons, Ltd.     

Preparation and characterization of vinylidene chloride‐co‐vinyl chloride copolymer/fluorinated synthetic mica nanocomposites I thermal and mechanical properties studies

Poly(vinylidene chloride‐co‐vinylchloride)/organically modified fluorinated synthetic mica (MEE) (VDC‐VC/MEE) nanocomposites were prepared by melt blending of VDC‐VC copolymer with MEE, in the presence of dioctyl phthalate (DOP) which acted as a plasticizer and a cointercalating agent. The nanostructure, thermal, and dynamic mechanical properties of the VDC‐VC/MEE nanocomposites were studied by wide angle X‐ray diffractometer (WAXD), scanning electron microscope (SEM), transmission electron microscope (TEM), thermogravimetric analyzer (TGA), and dynamic mechanical analyzer (DMA). It was found that partially intercalated and partially exfoliated structures coexisted in VDC‐VC/MEE nanocomposities. Below 8 wt % MEE content, the intercalation effect of nanocomposites decreased with increasing the MEE content. Under a nitrogen atmosphere, VDC‐VC/MEE nanocomposites exhibited a single step thermal degradation behavior. The nanostructure of VDC‐VC/MEE can effectively prevent volatile gases from being released, and thus enhances its thermal stability. The thermal stability of VDC‐VC/MEE nanocomposites is strongly related to the morphology of nanocomposites and the degraded composites structure. DMA revealed a significant improvement in the storage modulus within the testing temperature range. The increase in storage modulus depends on the MEE content, which is attributed to the dispersed phase morphology. The glass transition temperature of VDC‐VC/MEE nanocomposites is affected by the chain mobility in the nanocomposites rather than the aggregative morphology. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1214–1225, 2008     

Waterborne trifunctionalsilane‐terminated polyurethane nanocomposite with silane‐modified clay

Trifunctional organosilane‐modified clay was synthesized and used to prepare waterborne trifunctionalsilane‐terminated polyurethane (WSPU)/clay nanocomposite dispersions in this study. Qualitative evidence of the presence of chemically attached silane molecules on clay were confirmed by Fourier transform infrared spectroscopy. The grafted amount and the grafting yield were determined by thermogravimetric analysis and the obtained results were in good agreement with the cation exchange capacity of pristine clay. X‐ray diffraction and transmission electron microscopy examinations indicated that the clay platelets are mostly intercalated or partially exfoliated in the SPU matrix with a d‐spacing of ～2.50 nm. Clay does not influence the location and peak broadness of the glass transition temperature of soft segment as well as hard segment domains in the WSPU/clay films. WSPU/clay dispersion with higher clay content exhibits a marginal increase in the average particle size, but silane modified clay has a pronounced effect compared with Cloisite 20A‐based nanocomposites. In addition, the incorporation of organophilic clay can also enhance the thermal resistance and tensile properties of WSPUs dramatically through the reinforcing effect. The improvement in water and xylene resistance of the silane modified clay nanocomposites proved that trifunctional organosilane can be used as effective modifiers for clays. Storage stability results confirmed that the prepared nanocomposite dispersions were stable. This method provides an efficient way to incorporate silane modified clay in SPU matrix. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2747–2761, 2007     

Polypeptide‐based nanocomposite: Structure and properties of poly(L‐lysine)/Na+‐montmorillonite

The feasibility of constructing polymer/clay nanocomposites with polypeptides as the matrix material is shown. Cationic poly‐L‐lysine · HBr (PLL) was reinforced by sodium montmorillonite clay. The PLL/clay nanocomposites were made via the solution‐intercalation film‐casting technique. X‐ray diffraction and transmission electron microscopy data indicated that montmorillonite layers intercalated with PLL chains coexist with exfoliated layers over a wide range of relative PLL/clay compositions. Differential scanning calorimetry suggests that the presence of clay suppresses crystal formation in PLL relative to the neat polypeptide and slightly decreases the PLL melting temperature. Despite lower crystallinity, dynamic mechanical analysis revealed a significant increase in the storage modulus of PLL with an increase in clay loading producing storage modulus magnitudes on par with traditional engineering thermoplastics. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2579–2586, 2002     

Effect of the γ‐form crystal on the thermal fractionation of poly(propylene‐co‐ethylene)

The effect of the γ‐form crystal on the thermal fractionation of a commercial poly(propylene‐co‐ethylene) (PPE) has been studied by differential scanning calorimetry (DSC) and wide‐angle X‐ray diffraction (WAXD) techniques. Two thermal fractionation techniques, stepwise isothermal crystallization (SIC) and successive self‐nucleation and annealing (SSA), have been used to characterize the molecular heterogeneity of the PPE. The results indicate that the SSA technique possesses a stronger fractionation ability than that of the SIC technique. The heating scan of the SSA fractionated sample exhibits 12 endothermic peaks, whereas the scan of the SIC fractionated sample only shows eight melting peaks. The WAXD observations of the fractionated PPE samples prove that the content of the γ‐form crystals formed during the thermal treatment of the SIC technique is much higher than that of the SSA treatment. The former is 57.4%, whereas the later is 12.6%. The effect of theγ‐form crystals on thermal fractionation ability is discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4320–4325, 2004