Toughening of polypropylene with styrene/ethylene‐butylene/styrene tri‐block copolymer: Effects of reactive and nonreactive compatibilization

The effects of compatibilization on the toughening of polypropylene (PP) by melt blending with styrene/ethylene‐butylene/styrene tri‐block copolymer (SEBS) in a twin‐screw extruder were investigated. The compatibilizers used were SEBS functionalized with maleic anhydride (SEBS‐g‐MA), PP functionalized with acrylic acid (PP‐g‐AA), and bifunctional compound p‐phenylenediamine (PPD). The effects of the compatibilization were evaluated through the mechanical properties as well as through the determination of the phase morphology of the blends by scanning electron microscopy. Reactive compatibilized blends show up to a 30‐fold increase in impact strength compared with neat PP; likely the result of the reaction of the bifunctional compound (PPD) with the acid acrylic and maleic anhydride groups, this increase in strength rendered both morphological and mechanical stability to these blends. The addition of PPD to the blends significantly changed their phase morphologies, leading to larger average diameters of the dispersed particles, probably as a result of the morphological stabilization at the initial processing steps during extrusion, with the occurrence of chemical reactions. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3466–3479, 2002     

Toughening and compatibilization of polypropylene/polyamide‐6 blends with a maleated–grafted ethylene‐co‐vinyl acetate

In this article, maleated–grafted ethylene‐co‐vinyl acetate (EVA‐g‐MA) was used as the interfacial modifier for polypropylene/polyamide‐6 (PP/PA6) blends, and effects of its concentration on the mechanical properties and the morphology of blends were investigated. It was found that the addition of EVA‐g‐MA improved the compatibility between PP and PA6 and resulted in a finer dispersion of dispersed PA6 phase. In comparison with uncompatibilized PP/PA6 blend, a significant reduction in the size of dispersed PA6 domain was observed. Toluene‐etched micrographs confirmed the formation of interfacial copolymers. Mechanical measurement revealed that the addition of EVA‐g‐MA markedly improved the impact toughness of PP/PA6 blend. Fractograph micrographs revealed that matrix shear yielding began to occur when EVA‐g‐MA concentration was increased upto 18 wt %. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99:3300–3307, 2006     

Toughening of polypropylene with styrene/ethylene‐butylene/styrene tri‐block copolymer: Effects of mixing condition and elastomer content

The effect of processing conditions and elastomer content on the toughening of Polypropylene (PP) by melt blending with styrene/ethylene‐butylene/styrene tri‐block copolymer (SEBS) in a twin‐screw extruder has been investigated. The parameters analyzed were: temperature profile, screw speed, and feed rate of the blend components. Their effect was evaluated through the mechanical properties (tensile strength and Izod impact resistance at room temperature) as well as the morphology of the dispersed phase by means of scanning electron microscopy (SEM). The results showed that the impact resistance increases with increasing rotor speed and feed rate and decreases when the temperature profile is increased. The parameter with the greatest effect on the mechanical properties was the variation in rotor speed. Despite the fact that impact resistance as high as 25 times that of neat PP has been achieved with blends containing 20 wt % SEBS, no significant modification in phase morphology has been observed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2185–2193, 2001     

Polypropylene/polypropylene‐grafted acrylic acid copolymer/ethylene–Acrylic acid copolymer ternary blends for hydrophilic polypropylene

Ternary blends of polypropylene (PP), a polypropylene‐grafted acrylic acid copolymer (PP‐g‐AA), and an ethylene–acrylic acid copolymer (EAA) were prepared by melt blending. The surfaces of films with different contents of these three components were characterized with contact‐angle measurements. Scanning electron microscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, and thermogravimetric analysis were used to characterize the microstructure, melting and crystalline behavior, and thermal stability of the blends. The contact angles of the PP/PP‐g‐AA blends decreased monotonically with increasing PP‐g‐AA content. With the incorporation of EAA, the contact angles of the PP/PP‐g‐AA/EAA ternary blends decreased with increasing EAA content. When the concentration of EAA was higher than 15 wt %, the contact angles of the ternary blends began to increase. Scanning electron microscopy observations confirmed that PP‐g‐AA acted as a compatibilizer and improved the compatibility between PP and EAA in the ternary blends. Differential scanning calorimetry analysis suggested that acrylic acid moieties could act as nucleating agents for PP in the polymer blends. Thermogravimetric analysis and differential thermogravimetry confirmed the optimal blend ratio for the PP/PP‐g‐AA/EAA ternary blends was 70/15/15. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 436–442, 2006     

Highly transparent thermoplastic elastomer from isotactic polypropylene and styrene/ethylene‐butylene/styrene triblock copolymer: Structure‐property correlations

Polypropylene (PP) is one of the most useful general purpose plastics. However, the poor transparency and brittleness of PP restricts its applications in the field of medical and personal care where silicone and polyvinyl chloride (PVC) are presently used. This work concentrates on developing highly transparent elastomeric PP blends and also thermoplastic elastomer by blending isotactic polypropylene (I‐PP) with styrene/ethylene‐butylene/styrene (SEBS) triblock copolymer. PP/SEBS blend derived from high melt flow index (MFI) PP and high MFI SEBS exhibit remarkable transparency (haze value as low as 6%) along with good percentage of elongation and processability. The reduction in difference of refractive index (RI) between PP and SEBS has been observed by blending SEBS with PP. The wide angle X‐ray diffraction studies show that there is significant reduction in the percentage crystallinity of PP by the addition of SEBS block copolymer. Temperature‐dependent polarized light microscopy studies reveal the reduction in spherulites size by the addition of SEBS block copolymer. Transmission electron micrographs show that the SEBS polymer forms a fine lamellar structure throughout the PP matrix with phase inversion at higher SEBS concentration. Development of phase morphology, crystalline morphology, and crystallinity in different blends has been analyzed and microstructure‐haze correlations have been developed. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Toughening and brittle‐tough transition in blends of an amorphous polyamide with a modified styrene/ethylene‐butylene/styrene triblock copolymer

Amorphous polyamide (aPA)/maleated styrene/ethylene‐butylene/styrene triblock copolymer (mSEBS) blends with a mSEBS content up to 25% were obtained in the melt state with the aim of toughening the notch sensitive pseudoductile matrix, and of studying the parameters that influence the morphology that leads to the brittle/tough transition. The increase in the T_g of the rubbery phase, which depended on the maleinized copolymer content, indicated the presence of reacted copolymers. These copolymers should decrease the interfacial tension, thus allowing the presence of a fine dispersed particle size. The impressive (27‐fold) toughness increase observed, which is among the largest observed in toughened blends, took place at 15% mSEBS content. The critical interparticle distance (τ_c) of the blends was smaller than that of polyamide 6 (PA6)/mSEBS blends tested at the same conditions. Having ruled out the possible influence of other parameters, the lower τ_c of the aPA/mSEBS blends of this study is attributed to their higher interfacial adhesion that was inferred by the calculation of the solubility parameters and by the measured interfacial toughness. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Material ductility and toughening mechanism of polypropylene blended with bimodal distributed particle size of styrene–ethylene–butadiene–styrene triblock copolymer at high strain rate

The material ductility and toughening mechanisms under high strain rate are characterized in the polypropylene (PP) blended with two different styrene–ethylene–butadiene–styrene triblock copolymer (SEBS) by the tensile tests at the nominal strain rates from 0.3 to 100 s^?1, fracture surface observations, interparticle distances, and the morphological finite element (FE) analyses. It is found that the bimodal‐distributed SEBS particle morphology enhances the impact material ductility by craze bands formation, which is caused by the stress interaction between large rubber particles with the highly elongated small rubber particles inside the fibrils of the craze. It is found that there are three conditions for craze bands formation. The first condition is that the total SEBS content is larger than 15 wt %. Second condition is that the weight ratio of small SEBS particles against total SEBS particles should be larger than 0.06. Third condition is that the interparticle distance of large SEBS particles should be larger than 100 nm. In the numerical aspects, the present constitutive law with the craze nucleation and growth can successfully predict the craze bands in the microstructural FE models, leading to the useful procedure for identifying the ductile brittle transition based on the microstructure. The synergistic effect of these rubber particles gives rise to a strong increase in the ductility of these bimodal rubber particle distributed PP systems. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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     

Properties of dynamically vulcanized ethylene–propylene–diene copolymer/polypropylene blends

In this study, vulcanized thermoplastic elastomers were produced through the formation of crosslinks with peroxide for different ratios of ethylene–propylene–diene copolymer to polypropylene. Mixing was performed with a twin‐screw extruder. Afterward, the yield, tensile strength, elastic modulus, elongation, Izod impact strength, hardness, melt flow index, Vicat softening point, heat deflection temperature, and density of the crosslinks were determined. The thermal transition temperatures and microstructure were determined with differential scanning calorimetry and scanning electron microscopy, respectively. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3895–3902, 2007     

Morphology and thermal properties of maleic anhydride grafted polypropylene/ethylene–vinyl acetate copolymer/wood powder blend composites

Maleic anhydride grafted polypropylene (MAPP) was blended with ethylene–vinyl acetate (EVA) copolymer to form MAPP/EVA polymer blends. Wood powder (WP) was mixed into these blends at different weight fractions to form MAPP/EVA/WP blend composites. Differential scanning calorimetry (DSC) analysis of the blends showed small melting peaks between those of EVA and MAPP, which indicated interaction and cocrystallization of fractions of EVA and MAPP. The presence of MAPP influenced the EVA crystallization behavior, whereas the MAPP crystallization was not affected by the presence of EVA. Scanning electron microscopy, Fourier transform infrared spectroscopy, and DSC results show that the WP particles in the MAPP/EVA blend were in contact with both the MAPP and EVA phases and that there seemed to be chemical interaction between the different functional groups. This influenced the crystallization behavior, especially of the MAPP phase. The thermogravimetric analysis results show that the MAPP/EVA blend had two degradation steps. An increase in the WP content in the blend composite led to an increase in the onset of the second degradation step but a decrease in onset of the first degradation step. The presence of WP in the blend led to an increase in the modulus but had almost no influence on the tensile strength of the blend. The dynamic mechanical analysis results confirm the interaction between EVA and MAPP and show that the presence of WP only slightly influenced the dynamic mechanical properties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Differential scanning calorimetry of copolymer of isotactic polypropylene backbone with grafted poly(ethylene‐co‐propylene) branches

A series of graft polymers having polypropylene (PP) backbone and poly(ethylene‐co‐propylene) (EPR) side chains was prepared. PP backbone molecular weight (M_n) was 28–98 kg/mol, EPR side chain M_n was 2.6–17 kg/mol, and EPR content was 0–16 wt %. In this work, thermal analysis of the copolymers was performed using differential scanning calorimetry (DSC). Nonisothermal crystallization was performed at different cooling rates. The DSC thermograms revealed multiple melting peaks for slowly cooled samples, most likely the result of the melting of thinner tangential lamellae followed by the melting of thicker radial lamellae. Equilibrium melting temperature (T_m⁰) was determined using the linear Hoffman–Weeks method. Another approach was also used for determining T_m⁰: melting temperature (T_m) and crystallization temperature (T_c) were plotted as functions of logarithmic cooling rate. Linear relationships were observed for all samples with the cross points as T_m⁰'s. As cooling rate decreased, T_c, T_m, and enthalpy of fusion (ΔH_f) increased. T_m and T_m⁰ increased with increasing PP M_n. T_c and T_m were unaffected by the grafting of EPR onto the PP backbone. T_m⁰ and ΔH_f decreased as EPR content increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3380–3388, 2006     

Tensile behavior of polypropylene blended with bimodal distribution of styrene‐ethylene‐butadiene‐styrene particle size

The objective is to characterize the effects of the bimodal distribution of rubber particles and its blend ratio on the mechanical properties of the thermoplastic polypropylene blended with two different styrene‐ethylene‐butadiene‐styrene triblock copolymer at the intermediate and high strain rates. Tensile tests are conducted at the nominal strain rates from 3 × 10^?1 to 10² (1/s). Phase morphology is investigated to estimate the bimodal rubber particle size distribution. In addition, the in situ observation is conducted during uniaxially stretching within transmission electron microscopy step by step to investigate the deformation events depending on the elongation of samples. The elastic modulus increased gradually as the blend ratio of large rubber particle increased. An increase in the rupture strain and the strain energy up to failure was found for the bimodal rubber particle distributed blend system where the blend ratios of small rubber particle and large rubber particle were same. This is because the smaller particles dominant blend systems show the bandlike craze deformation while the localized plastic deformation is taken place in the larger particles dominated blend systems. The synergistic effect of these rubber particles gives rise to a strong increase in the ductility of these bimodal rubber particle distributed polypropylene systems. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Morphology and mechanical properties of polypropylene and poly(ethylene‐co‐methyl acrylate) blends

The morphology and mechanical properties of isotactic polypropylene (iPP) and poly(ethylene‐co‐methyl acrylate) (EMA) blends were investigated. Various EMA copolymers with different methyl acrylate (MA) comonomer content were used. iPP and EMA formed immiscible blends over the composition range studied. The crystallization and melting reflected that of the individual components and the crystallinity was not greatly affected. The size of the iPP crystals was larger in the blends than those of pure iPP, indicating that EMA may have reduced the nucleation density of the iPP; however, the growth rate of the iPP crystals was found to remain constant. The tensile elongation at break was greatly increased by the presence of EMA, although the modulus remained approximately constant until the EMA composition was greater than 20%. EMA with a 9.0% MA content provided the optimum effect on the mechanical properties of the blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 175–185, 2003     

Toughening isotactic polypropylene and propylene-ethylene block copolymer with styrene-ethylene butylene-styrene triblock copolymer

Dynamic mechanical properties, low-temperature impact behavior, flexural modulus and heat distortion temperature (HDT) of isotactic polypropylene (i-PP) and propylene-ethylene block copolymer (Co-PP) toughened with styrene-ethylene butylene-styrene triblock copolymer (SEBS), at blending ratios of 0–30 phr, were studied and compared. A scanning electron microscopic morphology study of the impact-fractured surfaces demonstrated the changes in fracture mechanisms at various temperatures and SEBS contents. SEBS remarkably improves the impact endurance in the lower-temperature range when blended with Co-PP in comparison with i-PP, due to the increased compatibility in the interface between SEBS particles and the Co-PP matrix.     

Thermo‐oxidative decomposition kinetics of elastomeric composites based on styrene‐(ethylene‐butylene)‐styrene triblock copolymer and organomontmorillonite

The elastomeric nanocomposites based on organomontmorillonite (OMMT) and styrene‐(ethylene‐butylene)‐styrene (SEBS) thermoplastic elastomer were prepared by melt processing using maleic anhydride grafted SEBS (SEBS‐g‐MA) as compatibilizer. Thermo‐oxidative decomposition behavior of the neat components and the nanocomposites were investigated using thermogravimertic analysis (TGA) in air atmosphere. The isoconversional method is employed to study the kinetics of thermo‐oxidative degradation. The heating modes and the composition of nanocomposites were found to affect the kinetic parameters (E_a, lnA and n). The E_a and lnA values of SEBS, OMMT, and their composites are much higher under dynamic heating than under isothermal heating. The reaction order (n) of OMMT was lower than those of SEBS and their composites. The obtained TG profiles and calculated kinetic parameters indicated that the incorporation of OMMT into SEBS significantly improved the thermal stability both under dynamic heating and under isothermal heating. The simultaneously obtained DSC data showed that the enthalpy of thermal decomposition decreased with OMMT loading. No significant change in the nonisothermal and isothermal stability of the nanocomposites with addition of SEBS‐g‐MA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Use of a sodium ionomer as a compatibilizer in polypropylene/high‐barrier ethylene–vinyl alcohol copolymer blends: The processability of the blends and their physical properties

The effect of a sodium ionomer (ion.Na⁺) on the compatibility of polypropylene (PP)/high‐barrier ethylene–vinyl alcohol copolymer (EVOH) blends was studied in terms of the thermal, mechanical, and optical properties and morphology. The rheological behavior, tensile tests, and morphology of the binary blends showed that the miscibility of EVOH with PP was very poor. The miscibility of the polymers improved with the ionomer addition. In general, the ion.Na⁺ concentration did not alter the thermal behavior of the blends, but it did improve the ductility of the injection‐molded specimens. Scanning electron micrographs displayed better adhesion between the PP and EVOH phases in the samples with the ionomer. The mechanical improvement was better in the film samples than in the injection‐molded samples. A 90/10 (w/w) PP/EVOH film with 5% ion.Na⁺ and an 80/20 (w/w) PP/EVOH film with 10% ion.Na⁺ presented better global properties than the other blends studied. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1763–1770, 2004     

Nonisothermal crystallization and multiple melting behaviors of β‐nucleated impact‐resistant polypropylene copolymer

As a substitute of isotactic polypropylene in applications requiring excellent fracture resistance, impact‐resistant polypropylene copolymer (IPC) has attracted much attention in recent years. In this study, a highly effective β‐form nucleating agent (β‐NA; an aryl amide compound) was introduced into IPC, and our attention was focused on the nonisothermal crystallization and subsequent melting behaviors of the nucleated samples. The nonisothermal crystallization behaviors were investigated on the basis of the different cooling rates and different concentrations of β‐NA with differential scanning calorimetry, wide‐angle X‐ray diffraction (WAXD), and polarized optical microscopy. The results show that both the cooling rate and concentration of β‐NA greatly determined the nonisothermal crystallization process and subsequent multiple melting behaviors. Further results show that the multiple melting behaviors were related to the transition in β crystallites and those between the β and α crystallites. The morphologies of the dispersed particles and the supermolecular structure of the matrix were characterized with scanning electron microscopy. Finally, the effect of the β‐NA concentration on the fracture resistance of IPC was evaluated by measurement of the notched Izod impact strength. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and characterization of polypropylene/clay nanocomposites with polypropylene‐graft‐maleic anhydride

Polypropylene (PP)/montmorillonite (MMT) nanocomposites were prepared by the esterification of propylene‐g‐maleic anhydride (MAPP) with MMT modified with α,ω‐hydroxyamines. The structural characterization confirmed the formation of ester linkages and the interaction between the silicate layers. In particular, X‐ray diffraction patterns of the modified clays and MAPP/MMT composites showed 001 basal spacing enlargement as great as 0.14–0.62 nm according to the type of α,ω‐hydroxyamine. Thermal characterization by thermogravimetric analysis for the composites revealed increased onset temperatures of thermal decomposition. The melting peak temperature decreased, and the crystallization peak temperature increased; this indicated that MMT retarded the crystallization of MAPP. Compounding PP with MAPP/MMT composites enhanced the tensile modulus and tensile strength of PP. However, the elongation at break decreased drastically even when the MMT content was as low as 0.4–2.0 wt %. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1229–1234, 2005     

Negative air ion releasing properties of tourmaline/bamboo charcoal compounds containing ethylene propylene diene terpolymer/polypropylene composites

The average concentrations of negative air ions (C_ion?) emitted from tourmaline (T), bamboo charcoal (B) particles, and tourmaline/bamboo charcoal (T/B) compounds containing polypropylene (PP) and ethylene propylene diene terpolymer/polypropylene (EPDM/PP) composite specimens under varying testing conditions were investigated in this study. The C_ion? values emitted from T or B filled PP and EPDM/PP composite specimens reached a maximum value as their T or B contents approached the 5 and 3 wt % optimum values, respectively. In contrast, the C_ion? values of T/B compounds filled PP and EPDM/PP composite specimens were significantly higher than their theoretical C_ion? values estimated using the “simple mixing rule,” and reached a maximum value as the weight ratio of T to B reaches an optimum value. At this optimum T/B weight ratio, the C_ion? values of T/B compounds filled PP and EPDM/PP composite specimens reached another maximum as their total compound loadings reached the optimum loading of 6 and 4 wt %, respectively. The C_ion? values of the PP/T/B and EPDM/PP/T/B specimens increased significantly as they were tested under dynamic mode or by increasing the testing temperatures. The T and/or T/B powders filled PP and EPDM/PP specimens exhibited significantly higher tensile strength (σ_f) and elongation at break (ε_f) values than did the B filled PP and EPDM/PP specimens with the same filler loadings, respectively. Energy dispersive X‐rays, particle size, and SEM morphology analysis of the filler particles present in the T, B, and T/B filled composite specimens were performed to understand these interesting negative air ion and tensile properties. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

苯乙烯-二元乙丙橡胶嵌段共聚物增韧聚丙烯

考察了苯乙烯-二元乙丙橡胶嵌段共聚物（SEP）和三元乙丙橡胶（EPDM）对聚丙烯（PP）的增韧作用。结果表明，SEP比EPDM具有更好的增韧效果。SEP以核-壳形态分布于PP基质中，有效地诱导PP基质产生银纹和剪切屈服，消耗大量的冲击能，SEP用量为10份时，PP/SEP共混材料的缺口冲击强度较纯PP的提高7-8倍，超过了20份EPDM增韧PP的效果，是一种新型的PP抗冲增韧改性剂。