Preparation and characterization of maleic anhydride‐g‐polypropylene/diamine‐modified clay nanocomposites

Polypropylene (PP)/montmorillonite (MMT) nanocomposites were prepared by compounding maleic anhydride‐g‐polypropylene (MAPP) with MMT modified with α,ω‐diaminododecane. Structural characterization confirmed the formation of characteristic amide linkages and the intercalation of MAPP between the silicate layers. In particular, X‐ray diffraction patterns of the modified clay and MAPP/MMT composites showed 001 basal spacing enlargement as much as 1.49 nm. Thermogravimetric analysis revealed that the thermal decomposition of the composite took place at a slightly higher temperature than that of MAPP. The heat of fusion of the MAPP phase decreased, indicating that the crystallization of MAPP was suppressed by the clay layers. PP/MAPP/MMT composites showed a 20–35% higher tensile modulus and tensile strength compared to those corresponding to PP/MAPP. However, the elongation at break decreased drastically, even when the content of MMT was as low as 1.25–5 wt %. The relatively short chain length and loop structure of MAPP bound to the clay layers made the penetration of MAPP molecules into the PP homopolymer phase implausible and is thought to be responsible for the decreased elongation at break. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 307–311, 2005     

Compatibilization of polypropylene/nylon 6 blends with a polypropylene solid‐phase graft

The compatibilization of polypropylene (PP)/nylon 6 (PA6) blends with a new PP solid‐phase graft copolymer (gPP) was systematically studied. gPP improved the compatibility of PP/PA6 blends efficiently. Because of the reaction between the reactive groups of gPP and the NH₂ end groups of PA6, a PP‐g‐PA6 copolymer was formed as a compatibilizer in the vicinity of the interfaces during the melting extrusion of gPP and PA6. The tensile strength and impact strength of the compatibilized PP/PA6 blends obviously increased in comparison with those of the PP/PA6 mechanical blends, and the amount of gPP and the content of the third monomer during the preparation of gPP affected the mechanical properties of the compatibilized blends. Scanning electron microscopy and transmission electron microscopy indicated that the particle sizes of the dispersed phases of the compatibilized PP/PA6 blends became smaller and that the interfaces became more indistinct in comparison with the mechanical blends. The microcrystal size of PA6 and the crystallinity of the two components of the PP/PA6 blends decreased after compatibilization with gPP. The compatibilized PP/PA6 blends possessed higher pseudoplasticity, melt viscosity, and flow activation energy. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 420–427, 2004     

Compatibilization of side‐chain,thermotropic, liquid‐crystalline ionomers to blends of polyamide‐1010 and polypropylene

A novel side‐chain, liquid‐crystalline ionomer (SLCI) with a poly(methyl hydrosiloxane) main chain and side chains containing sulfonic acid groups was used in blends of polyamide‐1010 (PA1010) and polypropylene (PP) as a compatibilizer. The morphological structure, thermal behavior, and liquid‐crystalline properties of the blends were investigated by Fourier transform infrared, differential scanning calorimetry, thermogravimetric analysis, and scanning electron microscopy. The morphological structure of the interface of the blends containing SLCI was improved with respect to the blend without SLCI. The compatibilization effect of greater than 8 wt % SLCI for the two phases, PA1010 and PP, was better than the effects of other SLCI contents in the blends. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2749–2754, 2002; DOI 10.1002/app.10179     

Blends of i‐PP and SBS. II. Influence of in situ compatibilization on the mechanical properties

This article concerns the in situ compatibilization of immiscible isotatic polypropylene/styrene–butadiene–styrene triblock copolymer blends (i‐PP/SBS) by use of a reactive mixture. For this purpose, maleated PP (PP–MAH) and SBS (SBS–MAH) were used as functionalized polymers and 4,4′‐diaminediphenylmethane was used as a coupling agent between maleated polymers, resulting in a graft copolymer. Binary blends of i‐PP/SBS, nonreactive ternary blends of i‐PP/PP–MAH/SBS, and reactive ternary blends of i‐PP/PP–MAH/SBS–MAH with varying diamine/anhydride molar ratios were prepared. The mechanical properties of the blends were determined by tensile and impact‐resistance tests. The optimum improvement in the mechanical properties was found when the diamine/anhydride molar ratio in the ternary reactive blends was 0.5/1. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 516–522, 2003     

Modification of the polarity and adhesive properties of polyolefins through blending with maleic anhydride grafted Fischer–Tropsch paraffin wax

The modification of the polarity and adhesive properties of linear low‐density polyethylene, low‐density polyethylene, and isotactic polypropylene through blending with paraffin wax (Fischer–Tropsch synthesis), grafted by maleic anhydride, was investigated. Maleic anhydride grafted paraffin wax significantly increased the polar component of the total surface free energy of polyolefins. Modified polyolefins also had significantly higher adhesion to the polar substrate, a crosslinked, epoxy‐based resin. The conservation of the good mechanical properties of the blends was observed up to 10 wt % wax, except for isotactic polypropylene blends, for which there was a reduction in the stress and strain at break at wax concentrations higher than 5%. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3069–3074, 2006     

Mechanical,thermal, and morphological properties of maleic anhydride‐g‐polypropylene compatibilized and chemically modified banana‐fiber‐reinforced polypropylene composites

Composites were prepared with chemically modified banana fibers in polypropylene (PP). The effects of 40‐mm fiber loading and resin modification on the physical, mechanical, thermal, and morphological properties of the composites were evaluated with scanning electron microscopy (SEM), thermogravimetric analysis (TGA), Infrared (IR) spectroscopy, and so on. Maleic anhydride grafted polypropylene (MA‐g‐PP) compatibilizer was used to improve the fiber‐matrix adhesion. SEM studies carried out on fractured specimens indicated poor dispersion in the unmodified fiber composites and improved adhesion and uniform dispersion in the treated composites. A fiber loading of 15 vol % in the treated composites was optimum, with maximum mechanical properties and thermal stability evident. The composite with 5% MA‐g‐PP concentration at a 15% fiber volume showed an 80% increase in impact strength, a 48% increase in flexural strength, a 125% increase in flexural modulus, a 33% increase in tensile strength, and an 82% increase in tensile modulus, whereas the heat deflection temperature increased by 18°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Poly(propylene)–poly(propylene)‐grafted maleic anhydride–organic montmorillonite (PP–PP‐g‐MAH–Org‐MMT) nanocomposites. II. Nonisothermal crystallization kinetics

The nonisothermal crystallization kinetics of poly(propylene) (PP), PP–organic‐montmorillonite (Org‐MMT) composite, and PP–PP‐grafted maleic anhydride (PP‐g‐MAH)–Org‐MMT nanocomposites were investigated by differential scanning calorimetry (DSC) at various cooling rates. Avrami analysis modified by Jeziorny and a method developed by Mo well‐described the nonisothermal crystallization process of these samples. The difference in the exponent n between PP and composite (either PP–Org‐MMT or PP–PP‐g‐MAH–Org‐MMT) indicated that nonisothermal kinetic crystallization corresponded to tridimensional growth with heterogeneous nucleation. The values of half‐time, Z_c; and F(T) showed that the crystallization rate increased with the increasing of cooling rates for PP and composites, but the crystallization rate of composites was faster than that of PP at a given cooling rate. The method developed by Ozawa can also be applied to describe the nonisothermal crystallization process of PP, but did not describe that of composites. Moreover, the method proposed by Kissinger was used to evaluate the activation energy of the mentioned samples. The results showed that the activation energy of PP–Org‐MMT was much greater than that of PP, but the activation energy of PP–PP‐g‐MAH–Org‐MMT was close to that of pure PP. Overall, the results indicate that the addition of Org‐MMT and PP‐g‐MAH may accelerate the overall nonisothermal crystallization process of PP. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3093–3099, 2003     

Thermal characteristics and crystallinity of Ziegler–Natta isotactic polypropylene/metallocene isotactic polypropylene polyblended fibers

Ziegler–Natta isotactic polypropylene (ZN‐iPP) and metallocene isotactic polypropylene (m‐iPP) were extruded (in ratios of 75/25, 50/50, and 25/75) from one melt twin‐screw extruder to produce three ZN‐iPP/m‐iPP polyblended polymers and, subsequently, spin fibers. In this study, we examined the rheology of the ZN‐iPP/m‐iPP polyblended polymers and the thermal characteristics and crystallinity of the ZN‐iPP/m‐iPP polyblended fibers using gel permeation chromatography, rheometry, differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction, density gradient analysis, and extension stress–strain measurement. The apparent melt viscosity of the ZN‐iPP/m‐iPP polyblended polymers revealed positive‐deviation blends. The 50/50 blend of ZN‐iPP/m‐iPP had the highest apparent melt viscosity. For five samples, the complex melt viscosity decreased with the angular frequency, which represented typical non‐Newtonian behavior. The Cole–Cole plot, which consisted of the imaginary part of the complex melt viscosity versus the real part of the complex melt viscosity plot, of the ZN‐iPP/m‐iPP polyblended polymers showed a semicircular relationship with the blend ratios. It indicated that the ZN‐iPP/m‐iPP polyblended polymers were miscible. We analyzed the shear modulus data (G′ vs G″) by plotting them on a log–log scale. The plot revealed almost the same slopes for the ZN‐iPP/m‐iPP polyblended polymers, which indicated a good miscibility between the ZN‐iPP and m‐iPP polymers. The experimental DSC results demonstrate that the ZN‐iPP and m‐iPP polymers constituted a miscible system. The crystallinity and tenacity of the ZN‐iPP/m‐iPP polyblended fibers initially increased and then fell as the m‐iPP content increased. Meanwhile, the 50/50 blend of ZN‐iPP/m‐iPP had the highest crystallinity and tenacity. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of a maleic anhydride grafted polypropylene–butadiene copolymer and its application in polypropylene/styrene–butadiene–styrene triblock copolymer/organophilic montmorillonite composites as a compatibilizer

A maleic anhydride grafted propylene–butadiene copolymer (MPPB) was prepared. Fourier transform infrared spectroscopy and ¹H‐NMR results indicate that the maleic anhydride molecules reacted with the double bond in the butadiene unit of the propylene–butadiene copolymer (PPB), and the grafting percentage increased with the butadiene content in the initial copolymer. The gel permeation chromatography results show that the introduction of butadiene in the copolymer prevented the degradation of PPB. The MPPB was applied in polypropylene (PP)/styrene‐butadiene‐styrene triblock copolymer (SBS)/organophilic montmorillonite (OMMT) composites as a compatibilizer. In the presence of 10‐phr MPPB, the impact strength of the composite was improved by about 20%. X‐ray diffraction patterns indicated the formation of the β‐phase crystallization of PP in the presence of MPPB, and a significant decrease in the spherulite size was observed. Transmission electron microscopy (TEM) images showed that the OMMT was better dispersed in the matrix upon the inclusion of MPPB. A better distribution of the rubber phase and a rugged fracture surface were observed in the scanning electron microscopy images as the MPPB proportion was increased. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Morphology and mechanical properties of polypropylene/high‐impact polystyrene blends from postconsumer plastic waste

The compatibilizing effect of the triblock copolymer poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) (SEBS) on the morphological and mechanical properties of virgin and recycled polypropylene (PP)/high‐impact polystyrene (HIPS) blends was studied, with the properties optimized for rigid composite films. The components of the blend were obtained from municipal plastic waste, PP being acquired from mineral water bottles (PP_b) and HIPS from disposable cups. These materials were preground, washed only with water, dried with hot air, and ground again (PP_b) or agglutinated (HIPS). Blends with three different weight ratios of PP_b and HIPS (6:1, 6:2, and 6:3) were prepared, and three different concentrations of SEBS (5, 6, and 7 wt %) were used for investigations of its compatibilizing effect. Scanning electron microscopy showed that SEBS reduced the diameter of dispersed HIPS particles in the globular and fibril shapes and improved the adhesion between the disperse phase and the matrix. However, SEBS interactions with PP_b and HIPS influenced the mechanical properties of the compatibilized PP_b/HIPS/SEBS blends. An adequate composition of PP/HIPS, for both virgin and recycled blends, for applications in composite films with characteristics similar to those of synthetic paper was obtained with a minimal amount of SEBS and a maximal HIPS/PP ratio in the range of concentrations studied. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2861–2867, 2003     

Effect of epolene E‐43 as a compatibilizer on the mechanical properties of palm fiber–poly(propylene) composites

Composites of palm fibers and poly(propylene) (PP) were compounded in an extruder at 200°C. The composites were subsequently injection molded into standard tensile specimens for mechanical characterization. The fracture morphology of the specimens was analyzed by scanning electron microscopy. It was observed that the composite modulus increased with the increase of fiber content, indicating the existence of adhesion between PP and the much stiffer palm fibers. However, the adhesion was not satisfactory and resulted in a decrease in the composite tensile strength with fiber addition. The compatibilizer Epolene E‐43 was used to minimize this incompatibility between the wood fibers and the PP matrix. The maleated PP additive enhanced the fiber–matrix adhesion, resulting in an improvement in composite performance. Also, small fibers showed better mechanical properties than those of long fibers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2581–2592, 2004     

Influence of the zeolite type on the mechanical–thermal properties and volatile organic compound emissions of natural‐flour‐filled polypropylene hybrid composites

The physicomechanical properties, thermal properties, odor, and volatile organic compound (VOC) emissions of natural‐flour‐filled polypropylene (PP) composites were investigated as a function of the zeolite type and content. The surface area and pore structure of the natural and synthetic zeolites were determined by surface area analysis and scanning electron microscopy, respectively. With increasing natural and synthetic zeolite content, the tensile and flexural strengths of the hybrid composites were not significantly changed, whereas the water absorption was slightly increased. The thermal stability and degradation temperature of the hybrid composites were slightly increased with increasing natural and synthetic zeolite content. At natural and synthetic zeolite contents of 3%, the various odors and VOC emissions of the polypropylene/rice husk flour and polypropylene/wood flour hybrid composites were significantly reduced because of the absorption of the odor and VOC materials in the pore structures of the natural and synthetic zeolites. These results suggest that the addition of natural and synthetic zeolites to natural‐flour‐filled thermoplastic polymer composites is an effective method of reducing their odor and VOC emissions without any degradation of their mechanical and thermal properties. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Mechanical,rheological, thermal,and morphological properties of blends based on poly(propylene)/poly(propylene‐co‐1‐octene)/poly(ethylene‐co‐1‐octene)

The effect of addition of propylene copolymer, produced by metallocene catalysts, on the mechanical, rheological, and morphological properties of blends based on poly(propylene) (PP) and ethylene–1‐octene copolymer (EOC) was evaluated. It was observed that the addition of 2 wt % propylene–1‐octene copolymer (POC) improved the impact strength of the EOC/PP blends. The rheological analysis indicated that the addition of propylene copolymer produced materials with improved processability. Thermal and morphological analysis showed that the POC acts as a compatibilizer on the EOC/PP blends. © 2003 Wiley Periodicals, J Appl Polym Sci 89: 1690–1695, 2003     

Mechanical property and morphology comparison between the two blends poly(propylene)/ethylene‐propylene‐diene monomer elastomer and poly(propylene)/maleic anhydride‐g‐ethylene‐propylene‐diene monomer

The comparison of the mechanical properties between poly(propylene)/ethylene‐propylene‐diene monomer elastomer (PP/EPDM) and poly(propylene)/maleic anhydride‐g‐ethylene‐propylene‐diene monomer [PP/MEPDM (MAH‐g‐EPDM)] showed that the latter blend has noticeably higher Izod impact strength but lower Young's modulus than the former one. Phase morphology of the two blends was examined by dynamic mechanical thermal analysis, indicating that the miscibility of PP/MEPDM was inferior to PP/EPDM. The poor miscibility of PP/MEPDM degrades the nucleation effectiveness of the elastomer on PP. The observations of the impact fracture mode of the two blends and the dispersion state of the elastomers, determined by scanning electron microscopy, showed that PP/EPDM fractured in a brittle mode, whereas PP/MEPDM in a ductile one, and that a finer dispersion of MEPDM was found in the blend PP/MEPDM. These observations indicate that the difference in the dispersion state of elastomer between PP/EPDM and PP/MEPDM results in different fracture modes, and thereby affects the toughness of the two blends. The finer dispersion of MEPDM in the blend of PP/MEPDM was attributed to the part cross‐linking of MEPDM resulting from the grafting reaction of EPDM with maleic anhydride (MAH) in the presence of dicumyl peroxide (DCP). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2486–2491, 2002     

Polypropylene–nanosilica‐filled composites: Effects of epoxy‐resin‐grafted nanosilica on the structural,thermal, and dynamic mechanical properties

This article reports a comparative study of polypropylene (PP) nanocomposites synthesized with nanosilica (NS) and diglycidyl ether of bisphenol A, an epoxy‐resin‐grafted nanosilica (ENS), as nanofillers. These nanocomposites were prepared with the melt‐mixing method at a constant loading level of 2.5 wt %; this loading level was much lower than that used for fillers in conventional composites. The effects of pure NS and ENS on the thermal, structural, mechanical, and dynamic mechanical properties of PP were analyzed with wide‐angle X‐ray diffraction, transmission electron microscopy, thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis, and scanning electron microscopy. The transmission electron microscopy studies showed a better dispersion of ENS in the PP matrix, that is, in the polypropylene‐epoxy‐resin‐grafted nanosilica (PP–ENS) nanocomposite, in comparison with NS in the PP matrix, that is, in the polypropylene–nanosilica (PP–NS) nanocomposite. Also, the thermogravimetric analysis results showed a higher thermal stability for PP–ENS than PP–NS. Furthermore, the dynamic mechanical analysis studies showed an increase in the elastic modulus and glass‐transition temperature for PP–ENS with respect to PP–NS. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2117–2124, 2006     

Reactive melt blending of modified polyamide and polypropylene: Assessment of compatibilization by fractionated crystallization and blend morphology

The melting and crystallization behavior of nonreactive and reactive melt‐mixed blends of polypropylene and carboxylic‐modified polyamide (mPA) as the dispersed phase was investigated. It was found that the size of the mPA particles decreases and the crystallization behavior of the mPA particles changes in dependence on the mixing time of the blends with oxazoline‐modified PP (mPP). This indicates that an in situ reaction occurs between the oxazoline groups of mPP and the carboxylic acid groups of mPA, resulting in a compatibilizing effect. In blends with mPP, the crystallization of the dispersed mPA phase splits into two steps. Below a critical particle size, the mPA does not crystallize at temperatures typical for bulk crystallization. These finely dispersed mPA particles crystallize coincidently with the PP phase, and this part increases with increasing mixing time. Analysis of the crystallization heat of both steps in connection with the particle volume distribution permits the estimation of the critical particle size to be ≤4 μm. These investigations showed that the effect of fractionated crystallization can be used to follow the morphology development and to evaluate the efficiency of compatibilizing interfacial reactions during processing. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3445–3453, 2002     

Influence of varying fiber lengths on mechanical,thermal, and morphological properties of MA‐g‐PP compatibilized and chemically modified short pineapple leaf fiber reinforced polypropylene composites

Environmentally benign, low cost and abundantly available short pineapple leaf fibers (PALF), found mostly in the Tropical rain forest climates are ideal materials for manufacture of thermoplastic polymer‐matrix composites. Here, mechanical and thermal properties of composites of maleic anhydride grafted polypropylene (MA‐g‐PP) and chemically modified short PALF are studied as a function of different fiber lengths at 10 vol % fibers loading with fiber orientation in the longitudinal direction. The effects of fiber lengths and fiber loading on the morphological properties are assessed via observations by scanning electron microscopy. Fiber length of 6 mm oriented longitudinally at 10 vol % fibers loading in PP is the optimum and recommended composition, where 73% increase in impact properties, 37% increase in the flexural modulus, 33% increase in flexural strength, and 14% increase in vicat softening temperature are observed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Thermal polymerization of a brominated flame retardant in a glass‐fiber‐reinforced polypropylene—quantitative analysis

Pentabromobenzylacrylate (PBBA) is a possible candidate for use as a fire retardant (FR) in polypropylene (PP) composites. While PBBA imparts FR properties to the PP composite, it also affects adversely its mechanical properties. The FR may undergo thermal polymerization or grafting to the PP chains during processing. To study the effect of the different forms of FR (monomer, polymerized, or grafted) on composite properties, we have quantified the extent of FR polymerization and extent of grafting onto the PP chains. Fourier transform infrared microscopy was used in this work to determine the extent of polymerization and the spatial distribution of the FR. The latter was found to be homogeneous throughout the composite. Thermal polymerization of the FR during extrusion is varied mainly by the addition of an antioxidant. The grafting process of the FR onto PP depends on the degree of thermal polymerization, and therefore on the addition of antioxidant. The limiting value for grafting achieved at full polymerization is ～10% w/w. The grafted FR was found to have a significant effect on PP crystallinity, and hence it is expected to affect the mechanical properties as well. Bromine analysis indicates the FR has reacted with filler surfaces as well. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1506–1515, 2003     

Crystallization and dynamic mechanical properties of polypropylene/polystyrene blends modified with maleic anhydride and styrene

Polypropylene (PP)/polystyrene (PS) blends modified with reactive monomers, such as maleic anhydride (MAH) and styrene (St), and in situ formed PP/PS blends were prepared by melting extrusion. The crystallization and melting behavior and the dynamic mechanical properties of the PP/PS blends, including the structure of the grafted copolymer, were investigated with differential scanning calorimetry, dynamic mechanical analysis, and Fourier transform infrared. The results indicated that the addition of MAH hardly influenced the crystallization temperature of PP in the blends, but the addition of MAH and St increased the crystallization temperature of PP in its blends. The blends showed no remarkable variety for the melting temperature, but the shapes of the melting peaks were influenced by the addition of the reactive monomers. In addition, a significant increase in the storage and loss moduli of all the modified PP/PS blends was observed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2038–2045, 2005     

Mechanical properties and morphology of PP/ABS blends compatibilized with PP‐g‐2‐HEMA

Polypropylene (PP) and acrylonitrile–butadiene–styrene blends of different composition were prepared using a single‐screw extruder. The binary blend of PP/ABS was observed to be incompatible and shows poor mechanical properties. PP‐g‐2‐hydroxyethyl methacrylate (2‐HEMA) was used as a compatibilizer for the PP/ABS blends. The ternary compatibilized blends of PP/ABS/PP‐g‐2‐HEMA showed improvement in the mechanical properties. Electron micrographs of these blends showed a homogeneous and finer distribution of the dispersed phase. The mechanical performance increased particularly in the PP‐rich blend. The 2.5‐phr (part per hundred of resin) compatibilizer was observed to bring improvement to the properties. The suitability of various existing theoretical models for the predication of the tensile moduli of these blends was examined. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 72–78, 2003