Structural characterization of reactor blends of polypropylene and ethylene‐propylene rubber

Blends of isotactic polypropylene (PP), ethylene‐propylene rubber copolymer (EPR), and ethylene‐propylene crystalline copolymer (EPC) can be produced through in situ polymerization processes directly in the reactor and blends with different structure and composition can be obtained. In this work we studied the structure of five reactor‐made blends of PP, EPR, and EPC produced by a Ziegler‐Natta catalyst system. The composition of EPR was related to the ratio between ethylene and propylene used in the copolymerization step. The ethylene content in the EPR was in the range of 50–70 mol %. The crystallization behavior of PP and EPC in the blends was influenced by the presence of the rubber, and some specific interactions between the components could be established. By preparative temperature rising elution fractionation (P‐TREF) analysis, the isolation and characterization of crystalline EPC fractions were made. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2155–2162, 2004     

Melt rheology and morphology of uncompatibilized and in situ compatibilized nylon‐6/ethylene propylene rubber blends

Melt rheology and morphology of nylon‐6/ethylene propylene rubber (EPR) blends were studied as a function of composition, temperature, and compatibilizer loading. Uncompatibilized blends with higher nylon‐6 content (N90 and N95) and rubber content (N5 and N10) had viscosities approximately intermediate between those of the component polymers. A very clear negative deviation was observed in the viscosity–composition curve over the entire shear rate range studied for blends having composition N30, N50, and N70. This was associated with the interlayer slip resulting from the high‐level incompatibility between the component polymers. The lack of compatibility was confirmed by fracture surface morphology, given that the dispersed domains showed no sign of adhesion to the matrix. The phase morphology studies indicated that EPR was dispersed as spherical inclusions in the nylon matrix up to 30 wt % of its concentration. A cocontinuous morphology was observed between 30 and 50 wt % nylon and a phase inversion beyond 70 wt % nylon. Various models based on viscosity ratios were used to predict the region of phase inversion. Experiments were also carried out on in situ compatibilization using maleic anhydride–modified EPR (EPR‐g‐MA). In this reactive compatibilization strategy, the maleic anhydride groups of modified EPR reacted with the amino end groups of nylon. This reaction produced a graft copolymer at the blend interface, which in fact acted as the compatibilizer. The viscosity of the blend was found to increase when a few percent of modified EPR was added; at higher concentrations the viscosity leveled off, indicating a high level of interaction at the interface. Morphological investigations indicated that the size of the dispersed phase initially decreased when a few percent of the graft copolymer was added followed by a clear leveling off at higher concentration. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 252–264, 2004     

Radiation effects on poly(propylene) (PP)/ethylene–vinyl acetate copolymer (EVA) blends

Radiation effects on poly(propylene)/ethylene–vinyl acetate copolymer (PP/EVA) blends are discussed. Increasing the EVA content enhanced the crosslinking effect of radiation in PP/EVA blends. This effect was significant when the EVA content was ≥50% in PP/EVA blends that were exposed to γ‐ray irradiation in air. This phenomenon is discussed in relation to the compatibility, morphology, and thermal properties of PP/EVA blends. The results indicate that the effect is dependent on the compatibility, the increase in the amorphous region content, and the EVA content in PP/EVA blends. The possible mechanism of radiation crosslinking or degradation in irradiated PP/EVA blends was studied quantitatively by a novel method, a “step analysis” process, and thermal gravimetric analysis. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3420–3424, 2002     

Interphase layer formation in isotactic polypropylene/ethylene–propylene rubber blends

The influence of the interphase layer, formed by the introduction of an oil in ethylene–propylene rubber (EPR), on the structure and properties of isotactic polypropylene (iPP)/EPR blends was studied. The dispersity of the rubber phase in the iPP matrix did not depend on presence of oil. The melting temperature of iPP decreased with increasing content of oil‐extended EPR, and it did not change if the oil was absent. The compatibility parameter was determined from the dependency of the iPP melting point on the rubber content with the Nishi–Wang equation. A negative value of the parameter indicated a limited compatibility of iPP with oil‐extended EPR. The latter also reduced the temperature and heat of crystallization of iPP. The mechanical properties of iPP/EPR blends were investigated as functions of temperature and elongation rate. It appeared that elastic modulus and yield stress of the blends linearly depended on the logarithm of the elongation rate. Activation volumes, calculated with the Eyring equation, increased with increasing content of elastomer; moreover, this increase was more pronounced for the oil‐extended elastomer. It is suggested that the oil influenced the structure of the interphase layer and, accordingly, the characteristics of the iPP/EPR blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 249–257, 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     

Phase separation and crystallization behavior in extruded polypropylene/ethylene–propylene rubber blends

Liquid–liquid (L–L) phase separation and its effects on crystallization in polypropylene (PP)/ethylene–propylene rubber (EPR) blends obtained by melt extrusion were investigated by time‐resolved light scattering (TRLS) and optical microscopy. L–L phase separation via spinodal decomposition (SD) was confirmed by TRLS data. After L–L phase separation at 250°C for various durations, blend samples were subjected to a temperature drop to 130°C for isothermal crystallization, and the effects of L–L phase separation on crystallization were investigated. Memory of the L–L phase separation via SD remained for crystallization. The crystallization rate decreased with increasing L–L phase‐separated time at 250°C. Slow crystallization for the long L–L phase‐separated time could be ascribed to decreasing chain mobility of PP with a decrease in the EPR component in the PP‐rich region. The propylene‐rich EPR exhibited good affinity with PP, leading to a slow growth of a concentration fluctuation during annealing. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 695–700, 2001     

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     

Preparation and characterization of syndiotactic polystyrene/ethylene‐propylene copolymer blends

The reactive compatibilization of syndiotactic polystyrene (sPS)/oxazoline‐styrene copolymer (RPS)/maleic anhydride grafted ethylene‐propylene copolymer (EPR‐MA) blends is investigated in this study. First, the miscibility of sPS/RPS blends is examined by thermal analysis. The cold crystallization peak (T_cc) moved toward higher temperature with increased PRS, and, concerning enthalpy relaxation behaviors, only a single enthalpy relation peak was found in all aged samples. These results indicate that the sPS/RPS blend is miscible along the various compositions and RPS can be used in the reactive compatibilization of sPS/RPS/EPR‐MA blends. The reactive compatibilized sPS/RPS/EPR‐MA blends showed finer morphology than sPS/EPR‐MA physical blends and higher storage modulus (G') and complex viscosity (η*) when RPS contents were increased. Moreover, the impact strength of sPS/RPS/EPR‐MA increased significantly compared to sPS/EPR‐MA blend, and SEM micrographs after impact testing show that the sPS/RPS/EPR‐MA blend has better adhesion between the sPS matrix and the dispersed EPR‐MA phase. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2084–2091, 2002     

Blend compatibilizers based on silane‐ and maleic anhydride–modified polyolefins

Polypropylene (PP)/polyamide blends were compatibilized with PP modified with vinylsilane or maleic anhydride and ethylene–propylene random (EPR) copolymer modified with maleic anhydride. The thermal behavior, mechanical properties, and morphology of the blends were investigated. Thermal analysis showed that the polyamide crystallization temperatures shifted downward with all compatibilizers, whereas its melting behavior did not change. On the other hand, polypropylene crystallization temperatures shifted upward in all cases, except for blends containing EPR modified with maleic anhydride. Tensile strength and elongation at break increased for blends compatibilized with modified PP. Blends containing up to 7% of EPR modified with maleic anhydride did not show good yield stresses. The morphology of the blends showed a finer dispersion of the polyamide minor phase in the PP matrix. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2492–2498, 2003     

Studies on the blends of CO2 copolymer. IV. Natural rubber/poly(propylene carbonate) systems

The blends of a carbon dioxide copolymer, poly(propylene carbonate)(PPC) with natural rubber (NR), were prepared and their mechanical properties and morphology were studied. The optimum formulation blend was obtained by orthogonal experiments. The tensile strength of the blend containing 30 phr PPC was 18.9 MPa, with an elongation at break of 755%. The factors such as PPC and dicumyl peroxide content, PPC molecular weight, sulfur content, curing time, and curing temperature responsible for controlling the mechanical properties were discussed. Transverse electron micrographs showed a two‐phase structure for this blend. Gel content data revealed that PPC was crosslinked. The phase stability of PPC in the blend improved because of the interpenetrating new work structure. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2140–2144, 2002     

Effect of talc on the properties of polypropylene/ethylene/propylene/diene terpolymer blends

In the present study, the effect of talc content on the mechanical, thermal, and microstructural properties of the isotactic polypropylene (i‐PP) and elastomeric ethylene/propylene/diene terpolymer (EPDM) blends were investigated. In the experimental study, five different talc concentrations, 3, 6, 9, 12, and 15 wt %, were added to i‐PP/EPDM (88/12) blends to produce ternary composites. The mechanical properties such as yield and tensile strengths, elongation at break, elasticity modulus, izod impact strength for notch tip radius of 1 mm, and hardness with and without heat treatments and thermal properties, such as melt flow index (MFI), of the ternary composites have been investigated. The annealing heat treatment was carried out at 100°C for holding time of 75 h. From the tensile test results, an increased trend for the yield and tensile strengths and elasticity modulus was seen for lower talc contents, while elongation at break showed a sharp decrease with the addition of talc. In the case of MFI, talc addition decreased the MFI of i‐PP/EPDM blends. It was concluded that, taking into consideration, mechanical properties and annealing heat treatment, heat treatment has much more effect on higher yield and tensile strengths, elongation at break, elasticity modulus, impact strength, and hardness. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3033–3039, 2006     

Impact modification of polypropylene by ethylene propylene copolymer‐grafted maleic anhydride

Blends of polypropylene (PP) and ethylene propylene rubber (EPR) were studied. The effect of the level of rubber addition and the ethylene content is described. The results show that the viscosity of the PP, rubber content, ethylene content, and grafted EPR by maleic anhydride (MA) are important factors in controlling the blend properties. The miscibility and dynamic properties of the blends were studied by DMTA. Impact and tensile properties were also studied. SEM was used for the investigation of the phase morphology and rubber particle size and particle‐size distribution. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1257–1265, 1999     

New synthesis methods for polypropylene‐co‐ethylene‐propylene rubber

In this research, the reinforcement of polypropylene (PP) was studied using a new method that is more practical for synthesizing polypropylene‐block‐poly(ethylene‐propylene) copolymer (PP‐co‐EP), which can be used as a rubber toughening agent. This copolymer (PP‐co‐EP) could be synthesized by varying the feed condition and changing the feed gas in the batch reactor system using Ziegler–Natta catalysts system at a copolymerization temperature of 10°C. The ¹³C‐NMR tested by a 21.61‐ppm resonance peak indicated the incorporation of ethylene to propylene chains that could build up the microstructure of the block copolymer chain. Differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and dynamic mechanical analysis (DMA) results also confirmed these conclusions. Under these conditions, the morphology of copolymer trapped in PP matrix could be observed and the copolymer T_g would decrease when the amount of PP‐co‐EP was increased. DMA study also showed that PP‐co‐EP is good for the polypropylene reinforcement at low temperature. Moreover, the PP‐co‐EP content has an effect on the crystallinity and morphology of polymer blend, i.e., the crystallinity of polymer decreased when the PP‐co‐EP content increased, but tougher mechanical properties at low temperature were observed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3609–3616, 2007     

Elastic properties of cast films from propylene elastomers

Propylene‐rich ethylene–propylene copolymers (P‐E elastomers) made using metallocene catalysts exhibit excellent elastic properties, including high elongation to break and low tension set, particularly when blended with polyethylene or polypropylene and then compression molded. During film casting, the orientation imposed on a P‐E elastomer lowers the extensibility and elastic recovery of films prepared from either neat P‐E or P‐E blends. A reduction in elongation to break of P‐E films, with or without blending, was found to correlate with an increase in planar birefringence. The presence of dispersed phases of PP or high density polyethylene in P‐E blends, which are drawn into elongated ellipsoids aligned in the machine direction, further reduces the recovery of these P‐E blends. This reduction in elastic recovery for films made from P‐E blends with aligned ellipsoidal dispersions was attributed to strain amplification around the dispersed particles in accordance with finite element simulation results, and was directly related to the dispersion tip radius. Films from P‐E elastomer blended with high density polyethylene (high interfacial tension) were demonstrated to have lower planar orientation in addition to reduced dispersion deformation, and, therefore, better elastic properties, versus films in which the P‐E elastomer was blended with PP (low interfacial tension). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The functions of crystallizable ethylene‐propylene copolymers in the formation of multiple phase morphology of high impact polypropylene

The functions of crystallizable ethylene‐propylene copolymers in the formation of multiple phase morphology of high impact polypropylene (hiPP) were studied by solvent extraction fractionation, transmission electron microscopy (TEM), selected area electron diffraction (SAED), nuclear magnetic resonance (¹³C‐NMR), and selected reblending of different fractions of hiPP. The results indicate that hiPP contains, in addition to polypropylene (PP) and amorphous ethylene‐propylene random copolymer (EPR) as well as a small amount of polyethylene (PE), a series of crystallizable ethylene‐propylene copolymers. The crystallizable ethylene‐propylene copolymers can be further divided into ethylene‐propylene segmented copolymer (PE‐s‐PP) with a short sequence length of PE and PP segments, and ethylene‐propylene block copolymer (PE‐b‐PP) with a long sequence length of PE and PP blocks. PE‐s‐PP and PE‐b‐PP participate differently in the formation of multilayered core‐shell structure of the dispersed phase in hiPP. PE‐s‐PP (like PE) constructs inner core, PE‐b‐PP forms outer shell, while intermediate layer is resulted from EPR. The main reason of the different functions of the crystallizable ethylene‐propylene copolymers is due to their different compatibility with the PP matrix. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Partial replacement of EPR by GTR in highly flowable PP/EPR blends: Effects on morphology and mechanical properties

This research analyzes the effect of ground tire rubber (GTR) and a novel metallocene‐based ethylene–propylene copolymer (EPR), with high propylene content, on the morphology and mechanical behavior of ternary polymer blends based on a highly flowable polypropylene homopolymer (PP). The PP/EPR blends morphology, with very small domains of EPR dispersed in the PP matrix, indicates a good compatibility among these materials, which leads to a significant improvement on elongation at break and impact strength. The incorporation of EPR on the rubber phase of thermoplastic elastomeric blends (TPE) based on GTR and PP (TPE^GTR) has a positive effect on their mechanical performance, attributed to the toughness enhancement of the PP matrix and to the establishment of shell‐core morphology between the rubber phases. The mechanical properties of the ternary blends reveal that TPE^GTR blends allow the upcycling of this GTR material by injection molding technologies. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42011.     

Influence of the ethylene–(methacrylic acid)–Zn2+ ionomer on the thermal and mechanical properties of blends of poly(propylene) (PP)/ethylene–(vinyl alcohol) copolymer (EVOH)

The thermal and mechanical properties and the morphologies of blends of poly(propylene) (PP) and an ethylene–(vinyl alcohol) copolymer (EVOH) and of blends of PP/EVOH/ethylene–(methacrylic acid)–Zn²⁺ ionomer were studied to establish the influence of the ionomer addition on the compatibilization of PP/EVOH blends and on their properties. The oxygen transmission rate (O₂TR) values of the blends were measured as well. PP and EVOH are initially incompatible as was determined by tensile tests and scanning electronic microscopy. Addition of the ionomer Zn²⁺ led to good compatibility and mechanical behaviour was improved in all blends. The mechanical properties on extruded films were studied for 90/10 and 80/20 w/w PP/EVOH blends compatibilized with 10 % of ionomer Zn²⁺. These experiments have shown that the tensile properties are better than in the injection‐moulded samples. The stretching during the extrusion improved the compatibility of the blends, diminishing the size of EVOH domains and enhancing their distribution in the PP matrix. As was to be expected, the EVOH improved the oxygen permeation of the films, even in compatibilized blends. Copyright © 2004 Society of Chemical Industry     

Effect of dynamic crosslinking on impact strength and other mechanical properties of polypropylene/ethylene‐propylene‐diene rubber blends

The deformation and fracture behavior of several dynamic vulcanizate blends of isotactic polypropylene with ethylene‐propylene‐diene rubber (EPDM) was examined and compared with those of uncrosslinked blends of PP/EPDM. These blends were prepared by melt mixing in an internal mixer at 190°C in a composition range of 10–40 wt % EPDM rubber. The variation in yield stress, the strength of fibrils of the craze, and the number density of the EPDM rubber domains (morphology fixation) that are dominant factors for enhancing interfacial adhesion and toughness in dynamic vulcanizate blends were evaluated. The ductility and toughness of these materials were explained in light of the composition between crack formation and the degree of plastic deformation through crazing and shear yielding. The physicomechanical properties including the hardness, yield stress, Young's modulus, percentage elongation, impact strength, flexural strength, and flexural modulus of dynamic vulcanized blends were found to be consistent and displayed higher values compared with uncrosslinked blends. The nucleation effect of the crosslinked particles and the decrease of crystallinity of the EPDM rubber were also considered to contribute to the improvement in the impact strength. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2089–2103, 2000     

Effect of clay on the morphology of blends of poly(propylene) and polyamide 6/clay nanocomposites

PP/NPA6 blends composed of poly(propylene) (PP) and polyamide 6/clay nanocomposites (NPA6) were prepared by twin‐screw extrusion and melt‐drawn into ribbons by a ribbon extrusion process. The influence of clay on the morphology of PP/NPA6 ribbons was investigated by means of field‐emission scanning electron microscopy and optical microscopy. The results show that at low clay content (3, 5 wt%), NPA6 exhibited continuous lamellar structure in PP as pristine PA6 did in a PP/PA6 blend, but at a higher clay content (10 wt%) only ellipsoids or elongated ellipsoids were observed. In order to explain the morphological difference, two factors, ie the compatibilization effect and melt rheology, have been taken into consideration. It has been found that both factors, and probably mainly the variation in melt rheology, were responsible for the morphological difference in the PP/NPA6 blends with different clay contents under the extensional flow field. Copyright © 2004 Society of Chemical Industry     

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