Influence of Type of Vulcanization on Rheological and Thermal Properties of PP/NR Blends

Summary Rheological and thermal behavior of isotactic polypropylene (PP) and natural rubber (NR) blends were studied, with special reference to the type of vulcanization (dynamic and static). It was found that dynamic crosslinking of the NR phase increases the viscosity of the system, while it decreases crystallinity degree. Statically vulcanized blends show similar properties regardless curing time while dynamically vulcanized blends show enhanced properties if compared to the corresponding uncured blends.     

The Effect of Dicumyl Peroxide Vulcanization on the Properties & Morphology of Polypropylene/Ethylene-Propylene Diene Terpolymer/Natural Rubber Blends

ABSTRACT

This article discusses some properties such as tensile properties, chemical and oil resistance, gel content, crystallinity, and morphology of polypropylene (PP)/ethylene-propylene diene terpolymer (EPDM)/natural rubber (NR) blends. Dicumyl peroxide (DCP) was applied as a crosslinking agent. In terms of tensile properties, peroxide vulcanized blend shows higher tensile strength and tensile modulus (stress at 100% elongation, M₁₀₀) as compared with the unvulcanized blend. The elongation at break of the peroxide vulcanized blend is higher for the blend with NR rich content compared with the EPDM rich content. The improvements in chemical and oil resistance as well as gel content of peroxide vulcanized blends have also proved the formation of crosslinks in the rubber phase. Scanning electron microscopy (SEM) micrographs from the surface extraction of the blends support that the crosslinks have occurred during dynamic vulcanization. Dynamical vulcanization with DCP has decreased the percent crystallinity of blends that can be attributed to the formation of crosslinks in the rubber.     

Comparison of Rheological and Mechanical Behavior of Dynamically and Statically Vulcanized PP/SBS Blends

Summary Rheological behavior of dynamically and statically vulcanized blends of isotatic Polypropylene (PP) and 20% wt Styrene-Butadiene-Styrene block copolymer (SBS) was studied with reference to the effect of extrusion conditions, curing agents (sulphur, peroxide) and curing times. All blends showed pseudoplastic behavior. When using sulphur, a slight increase on melt viscosity was observed, showing no differences with vulcanization method or with pre-vulcanization time. With peroxide, melt viscosity changed drastically. Dynamically vulcanized blends with sulphur showed a noticeable rise on elongation at break as well as on toughness while those statically vulcanized showed very low values on these properties.     

Multifunctional peroxide as alternative crosslink agents for dynamically vulcanized epoxidized natural rubber/polypropylene blends

Commonly used dicumyl peroxide (DCP) in combination with coagent, triallyl cyanurate (TAC), as a crosslinking agent is well acceptable for dynamically vulcanized rubber phase of thermoplastic vulcanizates (TPVs). However, it generally produces volatile decomposition products, which cause a typical unpleasant smell and a blooming phenomenon. In this work, influence of two types of multifunctional peroxides: 2,4‐diallyloxy‐6‐tert‐butylperoxy‐1,3,5‐triazine (DTBT) and 1‐(2‐tert‐butylperoxyisopropyl)‐3‐isopropenyl benzene (TBIB), on properties of TPVs based on epoxidized natural rubber (ENR)/polypropylene (PP) blends were investigated. The conventional peroxide/coagent combinations, i.e., DCP/TAC and tert‐butyl cumyl peroxide (TBCP)/α‐methyl styrene (α‐MeS) were also used to prepare the TPVs for a comparison purpose. The TPVs with multifunctional peroxide, DTBT, provided good mechanical properties and phase morphology of small dispersed vulcanized rubber domains in the PP matrix which were comparable with the DCP/TAC cured TPVs. However, the TPVs with TBIB/α‐MeS and TBCP/α‐MeS showed comparatively low values of the tensile properties as well as rather large phase morphology. The results were interpreted by three main factors: the kinetic aspects of the various peroxides, solubility parameters of respective peroxide/coagent combinations in the ENR and PP phases, and the tendency to form unpleasantly smelling byproducts. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The control of miscibility of PP/EPDM blends by adding lonomers and applying dynamic vulcanization

The control of miscibility for isotactic polypropylene (PP) and ethylene-propylene-diene terpolymer (EPDM) has been attempted by adding poly(ethylene-comethacrylic acid) (EMA) ionomers and by applying dynamic vulcanization. The rheological properties, crystallization behavior, and morphology of the dynamically vulcanized EPDM/PP/ionomer ternary blends were investigated with a Rheometrics dynamic spectrometer (RDS), a differential scanning calorimeter (DSC), and a scanning electron microscope (SEM). Two kinds of EMA ionomers neutralized with different metal ions (Na⁺ and ZN⁺⁺) were investigated. Blends were prepared on a laboratory internal mixer at 190°C. Blending and curing were performed simultaneously, i.e., EPDM was vulcanized with dicumyl peroxide (DCP) in the presence of PP/ionomer. The composition of PP and EPDM was fixed at 50/50 by wt% and the contents of EMA ionomer were vaired from 5 to 20 parts based on the total amount of PP and EPDM. It was found that the addition of ionomers and the application of the dynamic vulcanization were effective in enhancing the miscibility of PP and EPDM. The structure of the blends was controlled by the following three component phases, i.e., the phase of the dynamially valcanized EPDM, PP, and Zn-neutralized ionomer. The ternary blends showed more miscibility than the PP/EPDM binary blend. This is due to the thermoplastic interpenetrating polymer network (IPN) of the ternary blends. The structure and properties of the ternary blends differed, depending on the types and contents of ionomer, i.e., the ternary blend containing Na-neutralized ionomer did not show a thermoplastic IPN structure clearly, even though the blend was prepared by dynamic vulcanization. The ternary blend containing Zn-neutralized ionomer clearly showed the behavior of a thermoplastic IPN when the contents of ionomer and DCP were 15 parts and 1.0 part, respectively.     

Effects of blend composition and dynamic vulcanization on the morphology and dynamic viscoelastic properties of PP/EPDM blends

The morphology and dynamic viscoelastic properties of isotactic polypropylene (PP) blended with oil-free/oil-extended ethylene–propylene–diene (EPDM) rubbers were studied. Unvulcanized and dynamically vulcanized blends with the compositions PP/EPDM = 50/50 and = 30/70 were investigated. The morphology was observed by phase contrasted atomic force microscopy. The dynamic viscoelastic properties were determined with a rheometer of plate–plate configuration. It was shown that the rheological behavior was strongly affected by both the composition and the morphology of the blends. Significant improvement in the flowability of the dynamically vulcanized blends was observed when oil-extended EPDM was used instead of the oil-free version. It was demonstrated that the rheological properties are mostly controlled by the elastomer phase at low frequencies, while in the high-frequency range the influence of PP becomes dominant. The peculiarities in the rheological behavior of the thermoplastic elastomers (uncured blends, TPE) and thermoplastic dynamic vulcanizates (TPV, dynamically cured blends) containing oil-extended EPDMs were traced to a limited compatibility between the PP and EPDM components in the melt. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Properties of Polypropylene (PP)/Ethylene-Propylene Diene Terpolymer (EPDM)/Natural Rubber (NR) Vulcanized Blends: The Effect of N,N-m-Phenylenebismaleimide (HVA-2) Addition

This paper discusses process development, tensile properties, morphology, oil resistance, gel content, and thermal properties of polypropylene (PP)/ethylene-propylene diene terpolymer (EPDM)/natural rubber (NR) vulcanized blends with the addition of N,N-m-phenylenebismaleimide (HVA-2) as a compatibilizer. Blends were prepared in several blend ratios in a Haake Polydrive with temperature and rotor speed of 180°C and 50 rpm, respectively. Results indicated that the combination of dicumyl peroxide (Dicup) with HVA-2 shows high torque development and stabilization torque as compared to the blend with Dicup vulcanization alone. In terms of tensile properties, the combination of Dicup with HVA-2 shows higher tensile strength, tensile modulus (M₁₀₀), elongation at break, oil resistance, and gel content in all blend ratios compared to similar vulcanized blends with Dicup without HVA-2 addition. Scanning electron microscope (SEM) micrographs of the blends support that the cross-linking and compatibilization occur during the process of the vulcanized blend containing HVA-2. In the case of crystallinity of the blends, the addition of HVA-2 in Dicup vulcanized blend revealed a tendency for the percentage of crystallinity (Xc) to decrease. The addition of HVA-2 in Dicup vulcanization also produced blends with good thermal stability dealing with the so-called coagent bridge formation.     

Influences of the phenolic curative content and blend proportions on the properties of dynamically vulcanized natural rubber/acrylonitrile–butadiene–styrene blends

The vulcanization of natural rubber (NR)‐blended acrylonitrile–butadiene–styrene (ABS) was carried out with a phenolic curing agent by a melt‐mixing process. The NR compound was first prepared before blending with ABS. The effects of the phenolic curative contents (10, 15, and 20 phr) and blend proportions (NR/ABS ratio = 50 : 50, 60 : 40, and 70 : 30) on the mechanical, dynamic, thermal, and morphological properties of the vulcanized NR/ABS blends were investigated. The tensile strength and hardness of the blends increased with increasing ABS content, whereas the elongation at break decreased. The strength property resulting from the thermoplastic component and the vulcanized NR was an essential component for improving the elasticity of the blends. These blends showed a greater elastic response than the neat ABS. The thermal stability of the blends increased with increasing ABS component. Scanning electron micrographs of the blends showed a two‐phase morphology system. The vulcanized 60 : 40 NR/ABS blend with 15‐phr phenolic resin showed a uniform styrene‐co‐acrylonitrile phase dispersed in the vulcanized NR phase; it provided better dispersion between the NR and ABS phases, and this resulted in superior elastic properties. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42520.     

Synergistic effect of gamma radiation and peroxide on dynamic vulcanization of thermoplastic vulcanizes based on (devulcanized rubber)/polypropylene

Devulcanized rubber (DR) with highly crystalline polypropylene (PP) was used to prepare thermoplastic vulcanizates on the basis of DR/PP (75/25) blends. Influences of the curing systems, dicumyl peroxide (DCP) and gamma radiation, were investigated by X‐ray diffraction and scanning electron microscopy techniques. The mechanical and thermal behaviors of the composites in different proportions were studied. We found that the elastic modulus and tensile strength of the thermoplastic vulcanizates exhibited higher values than unvulcanized material. This finding may be attributed to an improvement in DR dispersion as well as interaction networks between the PP matrix and DR in the presence of DCP and the formation of more stable linkages. Peroxide caused a degradation of the PP molecules. A higher level of DCP was used in the peroxide‐vulcanized system and caused greater influence on properties. The mechanical and thermal properties of the unirradiated and irradiated composites were evaluated. J. VINYL ADDIT. TECHNOL., 20:168–176, 2014. © 2014 Society of Plastics Engineers     

马来酸酐和苯乙烯接枝改性对天然橡胶/聚丙烯共混物物理机械性能的影响

用动态硫化法制备了天然橡胶(NR)/聚丙烯(PP)热塑性弹性体(TPV)。研究了马来酸酐/苯乙烯/过氧化二异丙苯(MAH/St/DCP)多单体熔融接枝交联改性及纳米二氧化硅用量对NR/PP TPV物理机械性能的影响,讨论了NR/PP TPV的重复加工性能。结果表明,当MAH/St/DCP用量为3.750/1.875/0.375质量份、纳米二氧化硅用量为3质量份时,NR/PP TPV的物理机械性能最好,达到了国内外有关通用橡胶/PP TPV的水平,并且具有较好的重复加工性能。     

Cure characteristics and mechanical properties of hydrogenated natural rubber/natural rubber blends

The cure characteristics and mechanical properties of blends consisting of hydrogenated natural rubber (HNR) and natural rubber (NR) blends were investigated. The HNR/NR blends at 50/50 wt ratio were vulcanized using various cure systems: peroxide vulcanization, conventional vulcanization with peroxide, and efficient vulcanization with peroxide. The HNR/NR vulcanizates cured by the combination of peroxide and sulfur donor (tetramethylthiuram disulfide, TMTD) in the efficient vulcanization with peroxide exhibited the best mechanical properties. It was also found that the hydrogenation level of HNR did not affect the tensile strength of the vulcanizates. The tensile strength of the blends decreased with increasing HNR content because of the higher incompatibility to cause the noncoherency behavior between NR and HNR. However, the HNR/NR vulcanizate at 50/50 wt ratio showed the maximum ultimate elongation corresponding to a co‐continuous morphology as attested to by scanning electron micrographs. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of some curatives on the properties of ethylene propylene diene rubber/polyethylene blends

A series of ethylene propylene diene rubber/polyethylene (EPDM/PE) blends has been prepared containing different weight fractions of PE up to 0.66. The blends were vulcanized with a sulphur system N-cyclohexyl-2-benzthiazol sulphenamide/sulphur (CBS/S), and a non-sulphur-system dicumyl peroxide (DCUP). The concentration of the latter has been changed from 1.5 phr up to 6 phr calculated on the total weight of the blend composition. It has been found that the maximum torque obtained from rheographs for blends vulcanized with the CBS/S system decreases markedly with increasing PE concentration in comparison with those vulcanized with peroxide. The E modulus obtained from the stress–strain diagram at 110 °C showed the role played by the crosslinking of PE, the E modulus for blends vulcanized by peroxide being higher than for samples vulcanized with CBS/S. In contrast, the values of E modulus of both samples are practically the same at room temperature and attain more than 40 MPa depending on the composition. The tensile strength at room temperature strongly increases with increasing the weight fraction of PE. It has also been confirmed that the melting point of the crystalline phase of PE decreases with increasing crosslinking density of PE. The shear modulus obtained from dynamic mechanical measurements is in accordance with that obtained from static mechanical measurements. © 1999 Society of Chemical Industry     

Effects of Composition and Dynamic Vulcanization on the Rheological Properties of PP/NBR Blends

Summary Rheological behavior of isotactic polypropylene (PP) and nitrile rubber (NBR) blends, in the composition range of 10–30-wt % NBR content were studied, with special reference to the effect of blend ratio, dynamic vulcanization and compatibilization. All blends were prepared in a twin-screw extruder. Capillary Rheometry was employed. Pseudoplastic behavior of blends was favored by increasing rubber content. The incorporation of NBR into PP lowered activation energies. Compatibilization of unvulcanized blends did not produce significant changes on flow behavior. Dynamically vulcanized blends provide unique processing characteristics that enable to perform well in both injection molding and extrusion. Received: 8 October 2002/Revised version: 3 March 2003/Accepted: 4 March 2003 Correspondence to M. Hernández     

The Effect of Dynamic Vulcanization on the Properties of Polypropylene/Ethylene-Propylene Diene Terpolymer/Natural Rubber (PP/EPDM/NR) Ternary Blend

The effects of dynamic vulcanization on the process development and some properties, such as tensile properties, swelling index, gel content, crystallinity, and morphology, of the polypropylene (PP)/ethylene-propylene diene terpolymer (EPDM)/natural rubber (NR) blends were investigated. Dynamically vulcanized blends show higher stabilization torque than unvulcanized blends. In terms of tensile properties, the tensile strength and tensile modulus (stress at 100% elongation, M₁₀₀) of the vulcanized blends have been found to increase as compared with the unvulcanized blends, whereas the elongation at break is higher in the blend with richer EPDM content. These results can be attributed to the formation of cross-linking in the rubber phase. The formation of cross-links in the rubber phase has also been proved by swelling index and gel content. The percentage of crystallinity of the blends is decreased by dynamic vulcanization. Scanning electron microscopy (SEM) micrographs from the surface extraction of the blends support that the cross-links occurred during dynamic vulcanization.     

Peroxide‐catalyzed swell grafting of maleic anhydride onto polypropylene

A new grafting method was developed to incorporate maleic anhydride directly onto solid‐state polypropylene powders. Maleic anhydride grafts altered the nonpolar characteristics of polypropylene so that much better mixing was achieved in blends and composites of polypropylene with many other polymers and fillers. Maleic anhydride was grafted onto polypropylene by the peroxide‐catalyzed swell grafting method, with a maximum extent of grafting of 4.60%. Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, scanning electron microscopy, tensile testing, and impact testing were used to characterize the isotactic polypropylene (iPP), maleic anhydride grafted polypropylene (MAH‐g‐iPP), and (isotactic polypropylene)/(calcium carbonate) composites (iPP/CaCO₃). The crystallinity and heat of fusion of the MAH‐g‐iPP decreased as the extent of grafting increased. The mechanical properties of the CaCO₃ filled polypropylene were improved by adding MAH‐g‐iPP as a compatibilizing agent. The dispersion of the fillers in the polymer matrix and the adhesion between the CaCO₃ particles and the polymer matrix were improved by adding the compatibilizer.     

The observation of PP/EVA blends in which isotactic PP was preradiated with different radiation absorbed doses

Isotactic polypropylene (PP) was preradiated by γ ray with different absorbed doses and subsequently blended with ethylene‐vinyl acetate (EVA) co‐polymer to prepare PP/EVA blends. The average molecular weight (M_n) of isotactic PP decreased with the increasing radiation absorbed dose, which indicated that high energy radiation of γ ray broke the isotactic long PP chains into shorter ones. The melt flow rate results evidenced that the processing ability of PP/EVA blends was continuously promoted with the increasing absorbed dose. The β crystal was obtained in the PP/EVA blends by the radiation method. The onset temperatures and peaks of crystallization of PP/EVA blends decreased slightly with the increasing radiation absorbed dose, while high energy radiation was inclined to enhance the crystallinity of PP/EVA blends. The Fourier transform infrared spectroscopy (FTIR) tests confirmed an interesting phenomenon that PP tended to move to the surface of the PP/EVA blends with the increasing radiation absorbed dose. Mechanical tests proved that the PP/EVA blends remained a comparative stable mechanical property under the absorbed dose of 30 kGy. The experimental results indicated that PP/EVA blend was a potential candidate for industrial applying. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45057.     

Partial replacement of NR by GTR in thermoplastic elastomer based on LLDPE/NR through using reactive blending: Its effects on morphology,rheological, and mechanical properties

Attempts have been made to use different amount of ground tire rubber (GTR) powder as a partial substitute for natural rubber (NR) in thermoplastic elastomer based on linear low‐density polyethylene (LLDPE, 60 wt%) and NR (40wt%). Maleic anhydride (MA) and dicumyl peroxide (DCP) were used, during melt mixing of the compound, to modify GTR and vulcanize the rubber phases of the blends. Morphology of the blends was studied by scanning electron microscopy and rheological behavior investigated through rheomechanical spectroscopy. Mechanical properties of the blends were also measured, and the effect of GTR concentration on properties was evaluated. Obtained results showed that modification of GTR with MA and using DCP in the blends containing GTR improves the bonding between GTR and matrix. This leads to a distinctive rheological behavior and enhances tensile strength and elongation at break compared to its corresponding simple blend. It can be said that using of MA and DCP during melt mixing of thermoplastic elastomers based on LLDPE/NR containing GTR, concludes to a better dispersion of GTR and formation of morphology similar to that of a dynamic vulcanized thermoplastic elastomer, which improves interfacial bonding between phases and causes a dramatically increase in mechanical properties. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

The Effects of Dynamic Vulcanization by Dicumyl Peroxide (DCP) and N,N-m-Phenylene Bismaleimide (HVA-2) on the Properties of Polypropylene (PP)/Ethylene-Propylene Diene Terpolymer (EPDM)/Natural Rubber (NR) Blends

ABSTRACT

This paper discusses some properties of the polypropylene (PP)/ethylene-propylene diene terpolymer (EPDM)/natural rubber (NR) blends, such as tensile properties, heat resistance, gel content, and morphology. Dicumyl peroxide (DCP) and N,N-m-phenylene bismaleimide (HVA-2) and their combination were applied in PP/EPDM/NR blends as cross-link agents. In terms of tensile properties, the combination of DCP with HVA-2 shows the highest tensile strength and elongation at break in all PP/EPDM/NR blend ratios compared to similar blends, except with DCP or HVA-2 alone. The addition of HVA-2 produced blends with good heat resistance, while the combination of DCP with HVA-2 shows the highest gel content dealing with the cross-links formation. SEM micrographs from the surfaces extraction of the blends support that the cross-links have occurred during dynamic vulcanization process.     

Influence of phase modifiers on morphology and properties of thermoplastic elastomers prepared from ethylene propylene diene rubber and isotactic polypropylene

A series of thermoplastic elastomers (TPEs) were prepared from a binary blend of ethylene propylene diene rubber (EPDM) and isotactic polypropylene (iPP) using different types of phase modifiers. The influence of sulphonated EPDM, maleated EPDM, styrene‐ethylene‐co‐butylene‐styrene block copolymer, maleated PP, and acrylated PP as phase modifiers showed improved physico‐mechanical properties (like maximum stress, elongation at break, moduli, and tension set). Scanning electron and atomic force microscopy studies revealed better morphologies obtained with these phase modified EPDM‐iPP blends. The dependence of the phase modifier type and concentration was optimized with respect to the improvement in physical properties and morphology of the blends. Physical properties, dynamic mechanical properties, and morphology of these blends were explained with the help of interaction parameter, melt viscosity, and crystallinity of the blends. Theoretical modeling showed that Kerner, Ishai‐Cohen, and Paul models predicted the right morphology–property correlation for the prepared TPEs. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers.     

In‐situ ultrasonic compatibilization of unvulcanized and dynamically vulcanized PP/EPDM blends

Dynamically vulcanized PP/EPDM blends were treated by high‐intensity ultrasonic waves during extrusion. These blends were compared with unvulcanized PP/EPDM blends that were treated by ultrasound during extrusion and then dynamically vulcanized. Die pressure and power consumption were measured. The effects of different gap sizes, ratio of components, and number of ultrasonic horns were investigated. The rheological properties, morphology and mechanical properties of the blends with and without ultrasonic treatment were compared. The results obtained indicated that ultrasonic treatment induced thermo‐mechanical degradation, causing enhanced molecular transport and chemical reactions at the interfaces, thus leading to in‐situ compatibilization, which is evident by the morphological and mechanical property studies. Processing conditions were established for enhanced in‐situ compatibilization of the PP/EPDM blends that were either originally dynamically vulcanized and then ultrasonically treated or first treated and then dynamically vulcanized. Polym. Eng. Sci. 44:2019–2028, 2004. © 2004 Society of Plastics Engineers.