Design,Synthesis and Characterization of 3,4-Dihydro-2H-pyran Containing Copolymer/Clay Nanocomposites

We introduce briefly surface modification of clay minerals, structure, properties and, characterization techniques of polymer-clay (PCN's) nanocomposites. Organically modified layered-silicates or nanoclays have become an attractive class of hybrid materials due to their prospective use in a great variety of applications from industry to health. For design, synthesis and characterization for potential biomedical nanocomposites, antitumor-active copolymer; poly(DHP-alt-MA) were used to prepare copolymer/clay nanocomposites. The functional copolymers, having a combination of rigid/flexible linkages and an ability of complex-formation with interlayered surface of organo-silicate, and their nanocomposites have been synthesized by interlamellar complex-radical copolymerization of intercalated monomer complexes of maleic anhydride (MA) and 3,4-Dihydro-2H-pyran (DHP) with three alkyl ammonium salts surface modified bentonite and monomer mixtures. Poly(DHP-alt-MA) pristine copolymer and poly(DHP-alt-MA)/organically modified bentonite nanocomposites were characterized by Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy (ATR-FTIR), HR-Raman, X-ray diffraction (XRD) and TEM methods.     

Electrical conductivity and polarization processes in nanocomposites based on isotactic polypropylene and modified synthetic clay

The direct‐current and alternating‐current electrical behavior of nanocomposites, formed by isotactic polypropylene partially modified with maleic anhydride and filled with different amounts of modified synthetic clay, has been studied; moreover, the conduction mechanisms and the relaxation processes that take place in the materials have been investigated. The nanocomposites containing small clay contents exhibit direct‐current insulating properties comparable to or even higher than those observed in the polymeric matrix. However, as the synthetic clay content increases, the ionic contribution to conductivity becomes considerable. The nanocomposites also show a slightly higher permittivity and loss factor than the host material because of the appearance of a thermally activated relaxation process in the frequency range of 10^?2 to 10² Hz at the investigated temperatures. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 705–713, 2007     

Morphology and gas barrier properties of polyethylene‐based nanocomposites

Nanocomposites were processed by melt blending two reference matrices, a metallocene polyethylene and a low density maleic anhydride‐grafted polyethylene with an organo‐modified montmorillonite. It was shown that the introduction of a maleated polyethylene compatibilizer was required to improve the clay nanoplatelet dispersion in the metallocene polyethylene‐based nanocomposites. Increasing the montmorillonite content led to a significant increase of the barrier properties. Interfacial agents such as oxidized paraffins were shown to be more effective to reduce the gas permeability than maleated polyethylene and the dependence of the gas transport properties was discussed not only as a function of the clay dispersion but also as a function of the clay/compatibilizer and compatibilizer/matrix interactions. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 431–440, 2006     

Preparation, structure, and properties of styrene-ethylene-butylene-styrene block copolymer/clay nanocomposites: Part II fracture behaviors

Styrene-ethylene-butylene-styrene block copolymer (SEBS)/clay nanocomposites were prepared via a melt mixing technique. Various amounts of two types of maleated compatibilizers, styrene-ethylene-butylene-styrene block copolymer grafted maleic anhydride (SEBS-g-MA) and polypropylene grafted maleic anhydride (PP-g-MA), were incorporated to improve the dispersion of commercial organoclay (denoted as 20A), respectively. PP-g-MA compatibilized system conferred higher tensile strength and tear strength (initiation condition) than SEBS-g-MA compatibilized system. At a fixed content of compatibilizers, the above mechanical properties were improved with increasing clay content as well. By relating tensile strength to tear strength (arrest condition), the average depth of flaw was in the range of 33.8 ± 3.4 μm, which successfully confirmed the extension of Rivlin and Thomas’s theory for conventional elastomers to thermoplastic elastomer/clay nanocomposites for the first time. Cutting strength of SEBS/clay nanocomposites gave an intermediate value when compared with crystalline plastics and conventional amorphous elastomers, which further signified the importance of micro-yielding of styrene domains, crystalline yielding of compatibilizer, and filler reinforcement even in the nano-fracture zone of deformation.     

Effect of molecular interactions on the performance of poly(isobutylene-co-isoprene)/graphene and clay nanocomposites

Poly(isobutylene-co-isoprene) (IIR)/graphene and cloisite10A nanocomposites were prepared successfully and the resulting mechanical, rheological and barrier properties were carefully evaluated and compared. Chemical treatments like maleic anhydride grafting were used to improve the dispersion of the clay in the IIR matrix. Blends with different loading (20, 40, 60, and 80 %) of maleic anhydride grafted poly(isobutylene-co-isoprene) (MA-g-IIR) and IIR were made to maintain a balance between the beneficial polarity induced by MA grafting and the inevitable decrease in molecular weight (due to chain scission) induced by the free radical grafting process. The highest moduli, tensile strength and elongation at break were achieved in the case of a 60:40 ratio of MA-g-IIR (grafting degree 0.75)/IIR mixture with 5 phr of cloisite 10A. IIR/graphene nanocomposites exhibited higher reinforcement (Young’s moduli) and lower gas permeability compared to the optimized clay nanocomposites with same weight percentage. The filler–elastomer and filler–filler interactions deduced from rheology, stress relaxation and Payne effect experiments emphasize the reinforcing ability in IIR/graphene and MA-g-IIR/clay. XRD, SEM and TEM results further substantiated the results from the obtained micro structure of the nanocomposites. The improved performances of IIR/MA-g-IIR/clay and IIR/graphene were successfully correlated with interactions between the filler platelets and elastomer chains occurring in the nanocomposites.     

Thermal properties and microhardness of HDPE/clay nanocomposites compatibilized by different functionalized polyethylenes

The calorimetric characteristics, the flammability, the thermal stability and the microhardness of polyethylene high density/clay nanocomposites (HDPE/clay) have been studied by differential scanning calorimetry, thermogravimetry, determination of limiting oxygen index and microhardness tests. The nanocomposites have been compatibilized by ethylene–acrylic acid copolymer (EAA), acrylic acid grafted HDPE (HDAA) and maleic anhydride grafted HDPE (HDMA). The clay was montmorillonite Cloisite 15A. The influence of the presence and the type of the compatibilizers on the properties of the nanocomposites has been evaluated. The results have shown that the thermal stability, the reduction of the flammability and the microhardness of HDPE/clay nanocomposites, compatibilized by HDAA and HDMA are higher than those for nanocomposite compatibilized by EAA. Moreover, the presence and the type of compatibilizer have negligible effect on the characteristics of the HDPE phase transitions. These results have been interpreted by the better clay dispersion and higher level of clay exfoliation in the presence of compatibilizers HDAA and HDMA, than those in the presence of EAA compatibilizer.     

Studies of ABS-graft-maleic anhydride/clay nanocomposites: Morphologies, thermal stability and flammability properties

ABS-g-MAH (maleic anhydride) with different grafting degree, ABS/OMT (organo montmorillonite) and ABS-g-MAH/OMT nanocomposites were prepared via melt blending. The grafting reaction, phase morphology, clay dispersion, thermal properties, dynamic mechanical properties and flammability properties were investigated. FTIR spectra results indicate that maleic anhydride was successfully grafted onto butadiene chains of the ABS backbone in the molten state using dicumyl peroxide as the initiator and styrene as the comonomer and the relative grafting degree increased with increasing loading of MAH. TEM images show the size of the dispersed rubber domains of ABS-g-MAH increased and the dispersion is more uniform than that of neat ABS resin. XRD and TEM results show that intercalated/exfoliated structure formed in ABS-g-MAH/OMT nanocomposites and the rubber phase intercalated into clay layers distributed in both SAN phase and rubber phase. TGA results reveal the intercalated/exfoliated structure of ABS-g-MAH/OMT nanocomposites has better barrier properties and thermal stability than intercalated ones of ABS/OMT nanocomposites. The T_g of ABS-g-MAH/OMT nanocomposites was also higher than that of neat ABS/OMT nanocomposites. The results of cone measurements show that ABS-g-MAH/OMT nanocomposites exhibit significantly reduced flammability when compared to ABS/OMT nanocomposites even at the same clay content. The chars of ABS-g-MAH/OMT nanocomposites were tighter, denser, more integrated and fewer surface microcracks than ABS/OMT residues.     

Nanotailoring of sepiolite clay with poly [styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene]: structure–property correlation

Poly [styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] (SEBS)/sepiolite clay nanocomposites are prepared by solvent casting method. Two types of schemes have been adopted to establish the compatibility between nonpolar polymer (SEBS) and needle‐like inorganic filler (sepiolite), either by polar modification of the nonpolar polymer or organic modification of the inorganic filler. Structure–property correlation of nanocomposites derived from two different approaches is compared. Structural and morphological analysis of nanocomposites has been investigated by Fourier transform infrared spectroscopy, X‐ray diffraction, field emission scanning electron microscopy and transmission electron microscopy. Fourier transform infrared result shows better compatibility between SEBS and modified sepiolite clay compared to maleic anhydride grafted SEBS and pristine sepiolite in their nanocomposites. Tensile strength and % elongation are found to increase by 32 and 105%, respectively, with the addition of just 3 parts per hundred parts of resin (phr) modified sepiolite clay to pristine SEBS matrix. Moreover, thermal stability has also improved by 96°C with similar loading. This work provides a new insight into the structure and thermo‐mechanical properties of novel SEBS–sepiolite clay nanocomposites. Copyright © 2017 John Wiley & Sons, Ltd.     

Production of nanocomposites of PET-montmorillonite clay by an extrusion process

Polyethylene terephthalate (PET) was mixed by extrusion with clay (montmorillonite) to produce nanocomposites. Additives (pentaerythrytol and maleic anhydride) were added to induce compatibility between the particles and the matrix. Thermal, mechanical and Theological properties of the nanocomposites were evaluated. The nanocomposites with additives presented improved mechanical strength. In shear, the viscoelastic properties decrease with rising particle concentration and additives content. The resulting new materiales present processing advantages and potential improvements in performance.     

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     

Preparation and properties of isobutylene–isoprene rubber–clay nanocomposites

Isobutylene isoprene rubber (IIR)‐clay nanocomposites have been prepared successfully by melt intercalation with maleic anhydride‐grafted IIR (Ma‐g‐IIR) and organophilic clay. In IIR‐clay nanocomposites, the silicate layers of the clay were exfoliated and dispersed into the monolayer. The nanocomposites exhibited greater gas barrier properties compared with those of Ma‐g‐IIR. When 15 phr clay was added, gas barrier properties were 2.5 times greater than those of Ma‐g‐IIR. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1182–1188, 2006     

Preparation and characterization of PP/clay nanocomposites based on modified polypropylene and clay

X‐ray diffraction and differential scanning calorimeter (DSC) methods have been used to investigate the crystallization behavior and crystalline structure of hexamethylenediamine (HMDA)‐modified maleic‐anhydride‐grafted polypropylene/clay (PP‐g‐MA/clay) nanocomposites. These nanocomposites have been prepared by using HMDA to graft the PP‐g‐MA (designated as PP‐g‐HMA) and then mixing the PP‐g‐HMA polymer in hot xylene solution, with the organically modified montmorillonite. Both X‐ray diffraction data and transmission electron microscopy images of PP‐g‐HMA/clay nanocomposites indicate that most of the swellable silicate layers are exfoliated and randomly dispersed into PP‐g‐HMA matrix. DSC isothermal results revealed that introducing 5 wt % of clay into the PP‐g‐HMA structure causes strongly heterogeneous nucleation, which induced a change of the crystal growth process from a three‐dimensional crystal growth to a two‐dimensional spherulitic growth. Mechanical properties of PP‐g‐HMA/clay nanocomposites performed by dynamic mechanical analysis show significant improvements in the storage modulus when compared to neat PP‐g‐HMA. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3242–3254, 2005     

Carboxylate clays: A model study for polypropylene/clay nanocomposites

Sodium-montmorillonite was intercalated by carboxylate salts to prepare carboxylate clays. The intercalation of sodium acetate doubles the clay basal spacing and no degradation of the carboxylate clay is noticed in the extrusion temperature range. These carboxylate clays were used to synthesize polypropylene-graft-maleic anhydride (PP-g-MA)/clay nanocomposites. Nanocomposites were also produced by a one-pot process using in situ prepared carboxylate clay. The carboxylate salts within the clay layers partially neutralize the maleic anhydride groups of the PP-g-MA matrix, in situ during the melt compounding. The ionic groups of the partially neutralized polymer offer favourable interactions with the clay, hence reinforcing the interfacial bond between the polymer and the clay and improving the composite properties. The use of carboxylate clay clearly improves the clay dispersion into the PP-g-MA matrix and improves the nanocomposite’s thermal and rheological properties.     

Nanocomposites of NLO chromophore‐modified layered silicates and polypropylene

Intercalation of guest species into layered inorganic solids is a method of producing ordered inorganic–organic assemblies with unique microstructures controlled by host–guest and guest–guest interactions. Smectite clay minerals, such as montmorillonite, having appropriate functional molecules in between the silicate layers are supposed to exhibit a wide range of novel characteristics. Nanocomposite material based on maleic anhydride‐grafted polypropylene and dye‐modified layered silicate was developed. Characteristics of organo‐modified montmorillonite particles and polymer/clay hybrids have been investigated through FTIR, SAXS, DSC, UV measurements, and transmission electron microscopy. The results of the intercalation process, structural characterization, and thermal properties will be discussed in comparison with the intercalation and nanocomposite preparation results. The intercalation was successfully conducted by the ion‐exchange method. It was shown that intercalated dibenzilidene acetone type chromophores exist in the clay galleries in an aggregated form, probably as J‐aggregates. This feature strongly effects on optical and nonlinear optical properties of nanocomposites. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2493–2502, 2005     

Polypropylene-clay nanocomposites: effect of compatibilizing agents on clay dispersion

In this work, polypropylene-clay nanocomposites are obtained and studied by using two different coupling agents, diethyl maleate and maleic anhydride. Two different clays, a commercial montmorillonite (Nanomer I30.TC) and a sodium bentonite purified and modified with octadecylammonium ions have also been used. The relative influence of each factor, matrix and clay modification, can be observed from structural analysis (SAXS, TEM) and mechanical properties. An explanation of the results is proposed according to the microstructure and chemical nature of the systems and the thermodynamic interactions operating during nanocomposite preparation.     

Structure and properties of polyamide‐6/vermiculite nanocomposites prepared by direct melt compounding

Polyamide‐6 (PA6)/vermiculite nanocomposites were fabricated through the direct melt compounding of maleic anhydride‐modified vermiculite (MAV) with PA6 in a twin‐screw extruder followed by injection molding. The structure and morphology of the nanocomposites were determined by X‐ray diffraction and scanning and transmission electron microscopy techniques. The results revealed the formation of intercalated and exfoliated vermiculite platelets in the PA6 matrix. Tensile measurement showed that the tensile modulus and strength of the nanocomposites tended to increase with increasing vermiculite content. The thermal properties of the nanocomposites were determined by dynamic mechanical analysis, differential scanning calorimetry, and thermogravimetry measurements. The storage modulus of the PA6–MAV nanocomposites increased to almost twice that of the neat PA6. The thermal stability of the nanocomposites increased dramatically, and this was associated with the addition of vermiculite. The effect of the addition of maleic anhydride on the formation of the PA6–vermiculite nanocomposites was examined. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2860–2870, 2002     

LDH as Nanofiller: Organic Modification and Dispersion in Polymers

Summary: Layered double hydroxide (LDH) is a relatively new class of layered crystalline clay materials to be used as nanofiller in various polymer matrices. We report here the organic modification of LDH by anionic surfactants having different sizes and functionalities. Subsequently, their dispersion in polymer is discussed and finally the characteristics of the polymer/LDH nanocomposites are investigated. LDH has been modified using regeneration method, which shows that irrespective of size and functionality of the anionic surfactant, organic modification can be carried out efficiently. However, it has been observed that alkyl sulfonate are more efficiently intercalated within LDH layers than other surfactants giving well defined crystal structure of the modified LDH. These modified LDH, when dispersed in polymers like maleic anhydride grafted polyethylene shows that not only the size of the surfactant, but also the functionality of the surfactant influences their dispersion in a non polar polymer matrix.     

STRUCTURING & RHEOLOGY OF MOLTEN POLYMER/CLAY NANOCOMPOSITES

The evolution and the origin of "solid-like state" in molten polymer/clay nanocomposites are studied. Using polypropylene/clay hybrid (PPCH) with sufficient maleic anhydride modified PP (PP-MA) as compatibilizer, well exfoliation yet solid-like state was achieved after annealing in molten state. Comprehensive linear viscoelasticity and non-linear rheological behaviors together with WAXD and TEM are studied on PPCH at various dispersion stages focusing on time,temperature and deformation dependencies of the "solid-like" state in molten nanocomposites. Based on these, it is revealed that the solid-structure is developed gradually along with annealing through the stages of inter-layer expansion by PP-MA,the diffusion and association of exfoliated silicate platelets, the formation of band/chain structure and, finally, a percolated clay associated network, which is responsible for the melt rigidity or solid-like state. The network will be broken down by melt frozen/crystallization and weakened at large shear or strong flow and, even more surprisingly, may be disrupted by using trace amount of silane coupling agent which may block the edge interaction of platelets. The solid-like structure causes characteristic non-linear rheological behaviors, e.g. residual stress after step shear, abnormal huge stress overshoots in step flows and, most remarkably, the negative first normal stress functions in steady shear or step flows. The rheological and structural arguments challenge the existing models of strengthened entangled polymer network by tethered polymer chains connecting clay particles or by chains in confined melts or frictional interaction among tactoids. A scheme of percolated networking of associated clay platelets, which may in band form of edge connecting exfoliated platelets, is suggested to explain previous experimental results.     

STRUCTURING ＆ RHEOLOGY OF MOLTEN POLYMER／CLAY NANOCOMPOSITES

The evolution and the origin of “solid-like state” in molten polymer/clay nanocomposites are studied. Using polypropylene/clay hybrid (PPCH) with sufficient maleic anhydride modified PP (PP-MA) as compatibilizer, well exfoliation yet solid-like state was achieved after annealing in molten state. Comprehensive linear viscoelasticity and non-linear rheological behaviors together with WAXD and TEM are studied on PPCH at various dispersion stages focusing on time,temperature and deformation dependencies of the “solid-like” state in molten nanocomposites. Based on these, it is revealed that the solid-structure is developed gradually along with annealing through the stages of inter-layer expansion by PP-MA,the diffusion and association of exfoliated silicate platelets, the formation of band/chain structure and, finally, a percolated clay associated network, which is responsible for the melt rigidity or solid-like state. The network will be broken down by melt frozen/crystallization and weakened at large shear or strong flow and, even more surprisingly, may be disrupted by using trace amount of silane coupling agent which may block the edge interaction of platelets. The solid-like structure causes characteristic non-linear rheological behaviors, e.g. residual stress after step shear, abnormal huge stress overshoots in step flows and, most remarkably, the negative first normal stress functions in steady shear or step flows. The rheological and structural arguments challenge the existing models of strengthened entangled polymer network by tethered polymer chains connecting clay particles or by chains in confined melts or frictional interaction among tactoids. A scheme of percolated networking of associated clay platelets, which may in band form of edge connecting exfoliated platelets, is suggested to explain previous experimental results.     

Preparation of poly(propylene)/clay layered nanocomposites by melt intercalation from pristine montmorillonite (MMT)

Poly(propylene)/clay nanocomposites were prepared by melt intercalation, using pristine montmorillonite (MMT), hexadecyl trimethyl ammonium bromide (C16), poly(propylene) (PP) and maleic acid (MA) modified PP (MAPP), The nanocomposites structure is demonstrated using X‐ray diffraction (XRD) and high resolution electronic microscopy (HREM). Our purpose is to provide a general concept for manufacturing polymer nanocomposites by melt intercalation starting from the pristine MMT. We found different kneaders (twin‐screw extruder or twin‐roll mill) have influence on the morphology of the PP/clay nanocomposites. Thermogravimetric analysis (TGA) shows that the thermal stability of PP/clay nanocomposites has been improved compared with that of pure PP. Copyright © 2003 John Wiley & Sons, Ltd.