Preparation and properties of styrene–ethylene–butylene–styrene block copolymer/clay nanocomposites: I. Effect of clay content and compatibilizer types

BACKGROUND: Polymer/clay (silicate) systems exhibit great promise for industrial applications due to their ability to display synergistically advanced properties with relatively small amounts of clay loads. The effects of various compatibilizers on styrene–ethylene–butylene–styrene block copolymer (SEBS)/clay nanocomposites with various amounts of clay using a melt mixing process are investigated. RESULTS: SEBS/clay nanocomposites were prepared via melt mixing. 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 various amounts of commercial organoclay (denoted as 20A). Experimental samples were analyzed using X‐ray diffraction and transmission electron microscopy. Thermal stability was enhanced through the addition of clay with or without compatibilizers. The dynamic mechanical properties and rheological properties indicated enhanced interaction for the compatibilized nanocomposites. In particular, the PP‐g‐MA compatibilized system conferred higher tensile strength or Young's modulus than the SEBS‐g‐MA compatibilized system, although SEBS‐g‐MA seemed to further expand the interlayer spacing of the clay compared with PP‐g‐MA. CONCLUSION: These unusual results suggest that the matrix properties and compatibilizer types are crucial factors in attaining the best mechanical property performance at a specific clay content. Copyright © 2007 Society of Chemical Industry     

Structure and properties of polypropylene/hydrotalcite nanocomposites

This article presents the study of the modification of the particle/matrix interface region and its effects on the structure and dynamic mechanical behavior of polypropylene (PP)/hydrotalcite nanocomposites prepared by melt extrusion. The interface modification was promoted by combinying the organophillization of the hydrotalcite particles with blending the PP with a maleic anhydride‐grafted‐PP (PP‐g‐MAH) or a maleic anhydride‐grafted‐poly(styrene‐co‐ethylenebutylene‐co‐styrene) (SEBS‐g‐MAH). Sodium dodecyl sulphate was used to promote the organophillization of the hydrotalcite particles. X‐ray diffraction (XRD) and transmission electron microscopy (TEM) showed a partially exfoliated hydrotalcite structure, with an increasing exfoliation being achieved by adding a compatibilizer and organo‐modifying the particles. Values of the Young's modulus (E), storage modulus (E′), maximum tensile strength (σ_max), neck propagation strength (σ_neck), and elongation at break (ε_b) were found to depend both on the nature of the particle matrix interface as well as on the type of compatibilizer. Also, nanocomposites prepared with the organophillized particles showed lower T_g and loss factor values. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Evaluation of polypropylene grafted with maleic anhydride and styrene as a compatibilizer for polypropylene/clay nanocomposites

Among modified Poly(propylene)s (PPs) grafted with polar monomers, PP grafted with maleic anhydride (PP-g-MAH) is known to be the most efficient compatibilizer for PP/clay nanocomposites, since it provides well-dispersed nanostructures and yields optimal physical properties of the nanocomposites. One drawback of this material, however, is that it becomes brittle and its viscosity decreases drastically, leading to nanocomposites with low toughness as the graft degree of MAH increases. Therefore, there is a limitation to increasing both stiffness and toughness of PP/clay nanocomposites with PP-g-MAH. In this study, we investigated the performance of a PP grafted with maleic anhydride and styrene (PP-g-MAH-St) as compatibilizers in PP/clay nanocomposites. It was found that the incorporation of styrene as a comonomer prevents molecular weight reduction of the PP main chain upon high loading of a radical initiator for high graft degree of MAH. The compatibilizers (PP-g-MAH-St) thus obtained show good compatibilizing performance in PP/clay nanocomposites. The PP/clay nanocomposites compatibilized by PP-g-MAH-St show both high stiffness and toughness, which is accomplished by using a compatibilizer of higher viscosity compared with PP-g-MAH.     

Evaluations of PP-g-GMA and PP-g-HEMA as a compatibilizer for polypropylene/clay nanocomposites

In this study, we investigated the performances of a hydroxy ethyl methacrylate grafted PP (PP-g-HEMA) and a glycidyl methacrylate grafted PP (PP-g-GMA) as compatibilizers in PP/clay nanocomposites. The compatibilizers were prepared by melt grafting with a radical initiator. Since the PP-g-MA is successfully and widely used in the PP/clay nanocomposites, we also studied three PP-g-MAs containing different amounts of MA and having different molecular weights for a comparison. PP/clay nanocomposites compatibilized by the PP-g-HEMA and the PP-g-GMA show a similar level of the clay interlayer distances with those of the PP-g-MAs. We also investigated the effect of molecular weights of the compatibilizers. In general, the compatibilizer of lower molecular weight was observed to exhibit lower performance as a compatibilizer. It is observed that an increase of polar group content in the modified PP (PP-g-HEMA, PP-g-GMA, and PP-g-MA) always accompanies the molecular weight reduction, which deteriorates the mechanical properties. Thus, we prepared the PP-g-HEMA and PP-g-GMA by incorporation of a styrene comonomer. The compatibilizers (PP-g-HEMA-co-styrene and PP-g-GMA-co-styrene) thus obtained show good performance as a compatibilizer in the PP/clay nanocomposites. We observed that the PP/clay composites containing the PP-g-HEMA-co-styrene and the PP-g-GMA-co-styrene have very well-balanced mechanical properties.     

Functionalized polypropylenes in the compatibilization and dispersion of clay nanocomposites

The preparation of polypropylene (PP) nanocomposites was studied using clay and three types of modified PP (m‐PP) as compatibilizers: diethyl maleate grafted PP (PP‐g‐DEM), maleic anhydride grafted PP (PP‐g‐MA), and PP grafted with carbamyl maleamic acid (PP‐g‐UMA). The clay was made organophylic by an acid treatment with octadecylamine. PP functionalization and blending were carried out in an internal mixer. Blends of PP containing 20 and 40 wt% each of the modified PP and 5 wt% of organophilic clay (IMt), in each case, were prepared. Samples were characterized by transmission electron microscopy (TEM), differential scanning calorimetry (DSC), optical microscopy, and mechanical testing. The presence of tactoid, intercalated and exfoliated structures was observed by TEM in all the samples containing clay and modified PP, which also showed improved mechanical properties with tensile modulus as much as three times that of PP. Melting temperature did not vary significantly with the addition of clay. However, because of the clay's nucleating effect, an increase in the crystallization temperature was observed, accompanied by a slight decrease in the degree of crystallinity. The best results were obtained when PP‐g‐MA was used as the compatibilizer; intermediate results were obtained with the use of PP‐g‐UMA, followed by the results obtained when PP‐g‐DEM was used. Property enhancements were obtained when a higher percentage of modified PP was employed. POLYM. COMPOS., 27:451–460, 2006. © 2006 Society of Plastics Engineers     

Extrusion of linear polypropylene–clay nanocomposite foams

This work presents new results on using organoclay with an appropriate polymeric compatibilizer as rheology‐modifying additives for extrusion foaming of a linear polypropylene (PP), which by itself does not display strain hardening in extensional flow of the melt. The uniaxial melt‐extensional viscosity behavior of several nanocomposites prepared with varying ratio of bound maleic anhydride to clay as well as varying compatibilizer molecular weight was investigated. A chemical‐blowing agent was used at a fixed concentration for foaming these nanocomposites in a single‐screw extruder. Among nanocomposites with similar levels of clay dispersion or intercalation, the ones that displayed significant strain hardening in the melt state along with slower crystallization led to extruded PP nanocomposite foams with smaller cell sizes and greater cell density by reducing cell coalescence. This was achieved with as little as 3 wt% organoclay and a high‐molecular weight PP‐g‐MA compatibilizer in linear PP. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Investigations on clay dispersion in polypropylene/clay nanocomposites using rheological and microscopic analysis

Morphology assessment plays an important role as the ultimate properties of the processed nanocomposites mainly depend upon the morphology. This study focuses on the evaluation of polypropylene/clay nanocomposite structure using rheological and transmission electron microscopic investigation. Melt processing of nanocomposite was carried out on a co‐rotating twin screw extruder. Maleic anhydride grafted polypropylene (PP‐g‐MA) was used as a compatibilizer to facilitate better mixing of clay in polypropylene. The effect of compatibilizer to clay ratio on dispersion was analyzed through rheological data. An increase in complex viscosity and storage modulus with increase in compatibilizer content is observed at lower frequency region. Shifting of crossover frequencies to a lower value also indicate better exfoliation. Improved exfoliated morphology was also corroborated by Cole–Cole and inverse loss tangent plots. Transmission electron microscopy (TEM) micrograph based unique statistical image analysis was carried out using ImageJ software. A compatibilizer to clay content of 2 : 1 was found to be the optimum composition which was further supported by dielectric and mechanical properties. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4464–4473, 2013     

Effects of polypropylene-g-(maleic anhydride/styrene) compatibilizer on mechanical and rheological properties of polypropylene/clay nanocomposites

To enhance the dispersibility of clay in polypropylene (PP) matrix, PP-g-(maleic anhydride/styrene) (MA/ST) was prepared as a compatibilizer by graft copolymerization of maleic anhydride (MA) and styrene (ST) with PP. The addition of ST was known to be effective in improving the graft degree. PP/clay nanocomposites with the compatibilizer were prepared by melt intercalation. The X-ray diffraction (XRD) peaks of (0 0 1) plane of the organo-modified montmorillonite (O-MMT) were shifted to lower angles by an addition of PP-g-(MA/ST), indicating the intercalation capability of PP-g-(MA/ST) in the silicate layers. Transmission electron microscopy (TEM) photographs showed that the O-MMT in the presence of PP-g-(MA/ST) was intercalated and partly exfoliated during melt mixing. The addition of O-MMT and PP-g-(MA/ST) improved the thermal stability, tensile and rheological properties of the nanocomposites.     

Effect of processing conditions on morphology and mechanical properties of compatibilized polypropylene nanocomposites

This work focuses on the influence of processing conditions on the nanocomposites structure, i.e. intercalated or exfoliated, and on the enhancement of mechanical properties of polypropylene (PP) nanocomposites. These nanocomposites were prepared using the melt intercalation technique in a co-rotating intermeshing twin screw extruder. In order to optimise processing conditions, both screw speed and barrel temperature profile were changed. The role of the compatibilizer (maleic anhydride grafted polypropylene) was also studied. The results obtained show that the barrel temperature is a very important parameter: using lower processing temperature, the apparent melt viscosity and, consequently, the shear stress are higher and, therefore, the exfoliation of the clay is promoted. Even using optimised processing conditions, exfoliation of clay can be achieved only when an high compatibility between polymer and clay exists: the PP nanocomposites containing maleic anhydride show an exfoliated structure and a sensible enhancement of mechanical properties while PP nanocomposites without compatibilizer show a structure mainly intercalated and a lower improvement of mechanical properties.     

Polypropylene/clay nanocomposites: An innovative one‐pot process

This work discloses a novel one‐pot preparation method of polypropylene (PP)/clay nanocomposites with high degree of clay delamination and improved thermal, mechanical and rheological properties. The in situ simultaneous synthesis of carboxylate clay from native clay and ionomer of PP‐graft maleic anhydride (PP‐g‐MA) through trihydrate sodium acetate addition, combined with water injection in the extrusion process, appears to be a valuable alternative to the use of organoclay for producing PP/PP‐g‐MA/clay nanocomposites. The influence of PP‐g‐MA graft content, and of its ionomer form, onto the clay dispersion has been especially investigated. PP‐g‐MA of low graft content is compared to a home‐made highly grafted PP‐g‐MA synthesized in the presence of N‐bromosuccinimide (NBS). The nanocomposites prepared by combining the use of NBS‐mediated PP‐g‐MA, trihydrate sodium acetate and water injection exhibit the highest clay dispersion. Thermal, rheological, and mechanical properties of the nanocomposites have been measured. POLYM. COMPOS., 36:644–650, 2015. © 2014 Society of Plastics Engineers     

Effects of compatibilizers and testing speeds on the mechanical properties of organophilic montmorillonite filled polyamide 6/polypropylene nanocomposites

In the present study, the fracture properties of different types of organophilic montmorillonite (OMMT) filled polyamide 6/polypropylene nanocomposites was investigated. Two types of compatibilizers, i.e., maleic anhydride grafted polypropylene (PP‐g‐MA) and maleic anhydride grafted styrene‐ethylene/butylene‐styrene (SEBS‐g‐MA) were used to compatibilize these systems. The tensile properties were studied through tensile test at two different testing speeds; 50 and 500 mm/min whereas the fracture properties were determined using single‐edge‐notch‐3 point‐bending (SEN‐3PB) specimens at three different testing speeds; 1, 100, and 500 mm/min. The presence of both PP‐g‐MA and SEBS‐g‐MA compatibilizers improved the tensile and fracture properties of nanocomposites due to the compatibilizing effect of both compatibilizers. SEBS‐g‐MA compatibilizer seemed to be more effective in improving the fracture toughness of nanocomposites than PP‐g‐MA especially at high testing speed. This was due to the elastomeric nature of SEBS‐g‐MA, which can provide a better toughening effect than the relatively harder PP‐g‐MA. POLYM. ENG. SCI., 50:1493–1504, 2010. © 2010 Society of Plastics Engineers     

Polypropylene/clay nanocomposites prepared by in situ grafting‐melt intercalation with a novel cointercalating monomer

Polypropylene (PP)/clay nanocomposites were prepared by melt‐compounding PP with organomontmorillonite (OMT), using maleic anhydride grafted polypropylene (PP‐g‐MA) as the primary compatibilizer and N‐imidazol‐O‐(bicyclo pentaerythritol phosphate)‐O‐(ethyl methacrylate) phosphate (PEBI) as the cointercalating monomer. X‐ray diffraction patterns indicated that the larger interlayer spacing of OMT in PP was obtained due to the cointercalation monomer having a large steric volume and the d‐spacing further increased with the addition of PP‐g‐MA, as evidenced by transmission electron microscopy. Thermogravimetric analysis revealed that the PEBI‐containing PP nanocomposites exhibited better thermal stability than PEBI‐free PP composites. Dynamic mechanical analysis demonstrated that the storage modulus was significantly enhanced, and the glass transition temperature (T_g) shifted slightly to low temperature with the incorporation of clay for PP/OMT hybrids. PEBI‐containing PP/OMT composites gave a lower T_g value because of the strong internal plasticization effect of PEBI in the system. Cone calorimetry showed that the flame‐retardancy properties of PP nanocomposites were highly improved with the incorporation of PEBI. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Rice husk/poly(propylene‐co‐ethylene) composites: Effect of different coupling agents on mechanical,thermal, and morphological properties

Poly(propylene‐co‐ethylene) composites with rice husk were prepared in a corotating intermeshing twin‐screw extruder using four different coupling agents. While modified maleic anhydrides such as maleated polypropylene (MAPP) and maleated polyethylene (MAPE) are commonly used as compatibilizers to improve interfacial adhesion between lignocellulosic filler and matrix, in this study, polypropylene grafted with acid comonomer (CAPP) and high‐density polyethylene grafted with acid comonomer (CAPE) were also used. The morphologies and the thermal and mechanical properties of the composites were characterized using scanning electron microscopy, thermogravimetric analysis, differential scanning analysis, tensile and impact tests. The results indicate that the base resin of the compatibilizer is an important factor in determining the effectiveness of compatibilizers for composites. Composites with PP‐based compatibilizers are more effective than PE‐based compatibilizers due to the improved wetting of the former compatibilizer in the matrix polymer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Influence of two compatibilizers on clay/PP nanocomposites properties

This article investigates the influence on mechanical properties of using a two compatibilizer system. Cloisite‐Na Clay (ClNa) was organically modified in different ways with a polyethermonoamine and maleated polypropylene (MA‐g‐PP) added as a second compatibilizer. A corotating twin‐screw extruder was used to obtain nanocomposites based on polypropylene via the melt intercalation technique. X‐ray diffraction and differential scanning calorimetric results showed that intercalated nanocomposites with improved thermal stability were obtained. Increases of 8% in tensile strength, 34% in modulus, and 20% in crystallinity were observed. Also an increase of 23% in creep properties was observed when using these two compatibilizer system and 1% clay. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Effect of ionomer on clay dispersions in polypropylene‐layered silicate nanocomposites

In this study, polypropylene (PP)/clay nanocomposites containing different concentrations of ethylene‐methacrylic acid ionomer (i.e. Surlyn®) were prepared, and the effect of ionomer on clay dispersion was studied via WAXD, rheology, SEM, and TEM. The role of the ionomer in the nanocomposites was compared with that of maleic anhydride grafted PP (PP‐g‐MA), which has been widely used as a compatibilizer in making PP/clay nanocomposites. With an increase in the concentration of compatibilizer, the position of d₀₀₁ peak of OMMT shifted toward a lower angle for PP‐g‐MA system, while the position remained almost unchanged for Surlyn system, in which a larger interlayer spacing (d₀₀₁) was found with respect to the former. In rheology, the addition of the ionomer led to a gradual increase in both moduli and complex viscosity, and the nonterminal behavior at low frequency was observed in both systems. In addition, the ternary hybrid containing 20 wt % Surlyn achieved the largest enhancement in relative viscosity, which was more than that of the nanocomposite prepared from pure Surlyn or pure PP, presumably indicative of the existence of strong interaction between the components. Finally, SEM and TEM micrographs demonstrated that exfoliated structure was preferred for PP/Surlyn/OMMT hybrids, while intercalated morphology for PP/PP‐g‐MA/OMMT. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 4024–4034, 2007     

A study on nanofiller effects of serpentine in polypropylene matrix

The nanocomposite materials were prepared using serpentine as filler and polypropylene (PP) as the matrix in the presence of maleic anhydride grafted polypropylene (PP‐g‐MA) compatibilizer. The melt intercalation was carried out following serpentine modification with a quaternary salt of cetyl‐trimethyl‐ammonium bromide. The structure of nanocomposites was shown by X‐ray diffraction (XRD) and transmission electron microscopy (TEM) studies. Thermal analysis performed by differential scanning calorimetry (DSC) demonstrated that the nanocomposites have higher percentage crystallinity when compared to neat PP. Dynamic mechanical analysis (DMA) revealed that the storage and loss moduli values of the nanocomposites are better than those of the matrix resin. Tensile properties of nanocomposites are significantly different from PP, e.g., the Young's modulus of the nanocomposite with 2 wt % serpentine and 6 wt % PP‐g‐MA (PP‐2,6Q) was found to be 2065 MPa, i.e., nearly 190.8% increase over the PP matrix. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Melt processing and characterization of polypropylene/pristine montmorillonite nanocomposite: Influence of compatibilizer and hyperbranched polymer

In the present investigation, nanocomposites of polypropylene (PP)‐montmorillonite (MMT) clay were prepared by a single‐step compounding method to study the influence of hyperbranched polyester (HBPE) on rheological and mechanical properties of PP composites in the presence of a compatibilizer. In service of this objective, polyvinylchloride‐grafted‐maleic anhydride (PP‐g‐MA) was used as a compatibilizer for hydrophobic PP and hydrophilic clay. Rheological property in terms of melt viscosity was examined by a Brabender torque rheometer. The composite's morphology was studied by scanning electron microscopy (SEM) and transmission electron microscopy (TEM), whereas the dispersion state of nanoparticles in the PP matrix was studied by X‐ray diffraction (XRD). The thermal behavior of nanocomposites was examined by differential scanning calorimetry (DSC). The analysis of results confirmed that the interactions among both additives significantly influenced the morphology, rheology, and thermomechanical properties of the nanocomposites. J. VINYL ADDIT. TECHNOL., 22:72–79, 2016. © 2014 Society of Plastics Engineers     

Polypropylene‐organoclay nanocomposite: Preparation,microstructure, and mechanical properties

A series of polypropylene (PP) nanocomposites containing 2, 4, and 6 wt % of an organophilic montmorillonite clay was prepared via direct melt mixing in the presence of maleic anhydride grafted polypropylene (PP‐g‐MAH) as compatibilizing agent. Microstructure characterization was performed by X‐ray diffraction analysis. Nanocomposites exhibited a 15 and 22% enhancement in tensile modulus and impact strength, respectively. The heat deflection temperature of PP nanocomposites was 36°C greater than for pure PP. Thermal and mechanical properties of nanocomposites were compared to properties of traditional PP‐talc and PP‐glass fiber composites. The results showed that the properties of nanocomposites improved compared to ordinary polypropylene composites. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effects of clay contents on the dynamic mechanical and rheological properties of polypropylene/MAH‐g‐POE/clay composites

A series of polypropylene/maleic anhydride grafted polypropylene octane elastomer (MAH‐g‐POE)/clay (PPMC) nanocomposites were prepared with a novel compatilizer MAH‐g‐POE and different contents of octadecyl amine modified montmorillonite, and the effects of clay contents on the dynamic mechanical and rheological properties of these PPMC composites were investigated. With clay content increasing, the characteristic X‐ray diffraction peak changed from one to two with intensity decreasing, indicating the decreasing concentration of the intercalated clay layers. The gradual decrease of crystallization temperature of PPMC composites with the increase of clay loading should be attributed to the preferred intercalation of MAH‐g‐POE molecules into clay interlayer during blending, which is also reflected by scanning electron microscopy observations. By evaluating the activation energy for the glass transition process of MAH‐g‐POE and polypropylene (PP) in the PPMC composites, it is found that clay intercalation could cause the restriction effect on the glass transition of both MAH‐g‐POE and PP, and this restriction effect appears stronger for PP and attained the highest degree at 5 wt % clay loading. The melt elasticity of PP could be improved apparently by the addition of MAH‐g‐POE, and 5 wt % clay loading is enough for further enhancing the elastic proportion of PP. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Compatibilization and toughening of immiscible ternary blends of polyamide 6, polypropylene (or a propylene—Ethylene copolymer), and polystyrene

In this work, typical ternary blends of three versatile polymers—polyamide 6, a propylene–ethylene copolymer (co‐PP), and polystyrene—were studied. As a compatibilizer, co‐PP with randomly dispersed minor ethylene units was multimonomer‐melt‐grafted in the presence of maleic anhydride, styrene, and dicumyl peroxide. The influence of the ethylene content in co‐PP and the blend composition on the performance was investigated. Scanning electron microscopy images showed an obvious decrease in the droplet size of the dispersed phase with increases in the compatibilizer content and number of ethylene units in co‐PP. Peaks of tan δ/temperature curves approaching the glass‐transition temperatures of the components were observed with dynamic mechanical thermal analysis. The improved mechanical properties implied good compatibility of the components in the blends. Significant toughening was achieved when the concentration of co‐PP was increased from 15 to 25 wt %: the elongation at break of the compatibilized blends increased dozens of times in comparison with the elongation at break of the uncompatibilized blends. The introduction of the multimonomer‐melt‐grafted co‐PP was shown to be an effective approach for improving immiscible multipolymer blends and to have practical potential. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011