In situ compatibilization of PP/EPDM blends during ultrasound aided extrusion

Blends of isotactic polypropylene (iPP) and uncured ethylene-propylene diene rubber (EPDM) of various concentrations were treated by high power ultrasonic waves during extrusion. Die pressure and power consumption were measured. The effects of different gap sizes, blend ratios and number of ultrasonic horns were investigated. The rheological properties, morphology and mechanical properties of the blends with and without ultrasonic treatment were studied. In situ compatibilization of the blends was observed as evident by their more stable morphology after annealing, improved mechanical properties and IR spectra. The obtained results indicated that ultrasonic treatment induced the thermo-mechanical degradations and led to the possibility of enhanced molecular transport and chemical reactions at the interfaces. Processing conditions were established for enhanced in situ compatibilization of the PP/EPDM blends.     

Optimized processing conditions for the preparation of dynamically vulcanized EPDM/PP thermoplastic elastomers containing PP resins of various melt indexes

We have investigated the mechanical and morphological properties of un‐vulcanized and dynamically vulcanized ethylene propylene diene terpolymer/polypropylene (EPDM/PP) thermoplastic elastomers prepared under various processing conditions and possessing various compositions. After melt‐blending EPDM and PP resins twice in a twin‐screw extruder, the values of tensile strength (σ_f) of the un‐vulcanized EPDM/PP samples were at most equal to that of the pure EPDM specimen, but were much lower than those of the pure PP specimens. The elongations at break (ε_f) of the un‐vulcanized EPDM/PP samples were, however, dramatically higher than those of their respective virgin PP resins, and they improved significantly upon increasing the shear viscosity (η_s) of the PP resins. The tensile properties of the dynamically vulcanized EPDM/PP samples were significantly better than those of the corresponding un‐vulcanized EPDM/PP specimens. Similar to the behavior of the un‐vulcanized EPDM/PP specimens, the tensile properties of the dynamically vulcanized EPDM/PP specimens were optimized when prepared at a screw rate of 115 rpm. Morphological analysis revealed that the un‐vulcanized and dynamically vulcanized EPDM/PP specimens both featured many EPDM domains finely dispersed in continuous PP matrices. Such domains were present on the surfaces of the dynamically vulcanized EPDM/PP specimens; the relative sizes of the vulcanized EPDM domains were minimized when the vulcanized EPDM/PP specimens were prepared at the optimal screw rate (115 rpm). In fact, under these conditions, the average sizes of the vulcanized EPDM domains decreased upon increasing the values of η_s of the PP resins used to prepare the vulcanized EPDM/PP specimens. To understand these interesting tensile and morphological properties of the un‐vulcanized and dynamically vulcanized EPDM/PP specimens, we measured the rheological properties of the base polymers and performed energy‐dispersive x‐ray (EDX) analyzes of the compositions of the un‐vulcanized and dynamically vulcanized EPDM/PP specimens. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Ultrasonic treatment of polypropylene,polyamide 6, and their blends

The mechanical and rheological properties of polypropylene (PP), polyamide 6 (PA6), and their blends treated by high‐intensity ultrasound during extrusion were investigated. A lower head pressure was achieved in the extrusion of these thermoplastics. The mechanochemical and sonochemical effects of ultrasound led to simultaneous ionic condensation reactions and degradation in a homogeneous melt of PA6, with a prevailing effect of enhanced polycondensation reactions. The observed improvements in the mechanical properties of ultrasonically treated PA6 were attributed to condensation reactions, which yield a higher molecular weight, a higher crystallinity, and a more uniform crystal size distribution. At high ultrasound amplitudes, for PP, the degradation of polymer chains was observed with little deterioration of the mechanical properties. For ultrasonically treated PP/PA6 blends, a competition between the degradation and partial in situ compatibilization effect was found. At certain blend ratios, the tensile toughness and impact strength of the treated blends were almost double those of the untreated blends. However, full compatibilization was not achieved, possibly because of the low coupling selectivity of highly reactive radicals. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2643–2653, 2006     

Novel ultrasonic process for in‐situ copolymer formation and compatibilization of immiscible polymers

In‐situ copolymer formation and compatibilization of immiscible polymers in blends were discovered to occur during ultrasonic‐assisted extrusion in the melt state under high pressures. Residence times were of the order of seconds. The mechanical performance of plastic/rubber and rubber/rubber blends subjected to ultrasonic treatment was significantly enhanced compared to those of identical blends not subjected to ultrasonic treatment and having similar phase morphologies. The appearance of a high molecular weight tail in the rubber/rubber blends, stabilization of phase morphology in the melt state, the presence of a transition interface nanolayer and a decrease in the amount of extractable components in the plastic/rubber blends after ultrasonic‐assisted extrusion point towards the occurrence of in‐situ copolymer formation at the interfaces.     

动态硫化EPDM/PP共混物力学性能的研究

考察了硫黄用量和聚合物共混比对动态硫化ＥＰＤＭ／ＰＰ热塑性弹性体性能的影响。结果表明,随着硫黄用量增大,ＥＰＤＭ／Ｐ共混物的拉伸强度、１００％定伸应力和扯断伸长率先增大后减小、硬度有所增大,随着ＰＰ用量的增大,ＥＰＤＭ／ＰＰ共混物的拉伸强度、１００％定伸应力和硬度均有所增大,扯断伸长率也先大后减小。ＰＰ用量的变化对这些性能的影响更显。     

加工方法对动态硫化的聚丙烯/三元乙丙橡胶/甲基丙烯酸锌复合材料的力学性能影响

通过三种不同的加工手段,制备了动态硫化的聚丙烯(PP)/三元乙丙橡胶(EPDM)/甲基丙烯酸锌(ZDMA)复合材料。结果表明,Haake密炼机制备的复合材料综合性能较佳,并且较低的加工温度能够获得综合性能较好的PP/EPDM/ZDMA复合材料。力学性能的数据表明,EPDM的加入,在降低了PP拉伸强度的同时,增加了PP的韧性,而加入ZDMA则进一步提高了复合材料的冲击强度。     

振动力场强化动态全硫化EPDM/PP热塑性硫化胶的研究

介绍了动态三螺杆反应挤出机的结构特征,采用动态三螺杆反应挤出机对EPDM/PP共混物进行动态全硫化挤出,并对其制品的物理力学性能进行了测试分析以及微观结构的电镜扫描分析,结果表明,由于在动态全硫化挤出的全过程中引入了振动力场,经动态三螺杆反应挤出机动态全硫化挤出的热塑性硫化胶(TPV)具有优化的微观结构,力学性能优异。     

Effect of ultrasound on extrusion of PP/EPDM blends: Structure and mechanical properties

The effects of ultrasonic irradiation on the mechanical properties, morphology, and crystal structure of polypropylene (PP)/ethylene‐propylene‐diene terpolymer (EPDM) blends were examined. Results show that appropriate irradiation intensity can noticeably increase the toughness of the PP/EPDM blends without reducing rigidity. Scanning electron microscopic (SEM) observation shows that with ultrasonic irradiation, the morphology of a well‐dispersed EPDM phase is formed in the PP/EPDM blend. The glass transition temperatures of PP and EPDM phase approach each other as a result of ultrasonic irradiation. Differential Scanning Calorimetric (DSC) analysis indicates that the crystallinities of the PP and EPDM phases increase with ultrasonic irradiation, and β crystals of PP form in the PP/EPDM blend with ultrasonic irradiation, which is proven by wide angle X‐ray diffraction (WAXD) analysis. Polym. Eng. Sci. 44:1509–1513, 2004. © 2004 Society of Plastics Engineers.     

Compatibilized and dynamically vulcanized thermoplastic elastomer blends of poly(butylene terephthalate) and ethylene propylene diene rubber

Compatibilized and dynamically vulcanized thermoplastic elastomer blends of poly(butylene terephthalate) (PBT) and ethylene propylene diene terpolymer (EPDM) can be prepared by using an EPDM rubber that contains reactive epoxy groups. During melt mixing the epoxy groups react with PBT endgroups to form graft copolymer. The compatibilized blends can be dynamically vulcanized by conventional vulcanization agents for EPDM such as peroxides or by vulcanization agents that react with residual epoxy groups on the EPDM such as diamines. This paper describes the effects of compatibilization and dynamic vulcanization on microstructure and mechanical properties.     

Mechanical properties and structural characteristics of dynamically photocrosslinked PP/EPDM blends

The mechanical properties and crystal morphological structures of dynamically photocrosslinked polypropylene (PP)/ethylene‐propylene‐diene terpolymer (EPDM) blends have been studied by mechanical tests, wide‐angle X‐ray diffraction (WAXD), scanning electron microscopy (SEM), and differential scanning calorimetry (DSC). Dynamically photocrosslinking of PP/EPDM blends can improve the mechanical propertiess considerably, especially the notched Izod impact strength at low temperature. Data obtained from mechanical tests show that the notched Izod impact strength of a dynamically photocrosslinked sample with 30% EPDM at ?20°C is about six times that of an uncrosslinked sample with the same EPDM component. The results from the WAXD, SEM, and DSC measurements reveal the enhanced mechanism of impact strength for the dynamically photocrosslinked PP/EPDM blends as follows: (i) the β‐type crystal structure of PP is formed and the interplanar distance of β‐type crystal increases slightly with an increase in the EPDM component; (ii) the droplet size of the EPDM phase in the photocrosslinked PP/EPDM blends is obviously reduced and the droplet number is increased with an increase in the EPDM component during the dynamical photocrosslinking process; (iii) the graft copolymer of PP‐g‐EPDM is formed at the interface between PP and EPDM components. All the above changes from the crystal morphological structures are favorable for increasing the compatibility and enhancing the toughness of PP/EPDM blends at low temperatures.     

Mechanical properties,morphological structure,and thermal behavior of dynamically photocrosslinked PP/EPDM blends

A dynamically photocrosslinked polypropylene (PP)/ethylene–propylene–diene (EPDM) rubber thermoplastic elastomer was prepared by simultaneously exposing the elastomer to UV light while melt‐mixing in the presence of a photoinitiator as well as a crosslinking agent. The effects of dynamic photocrosslinking and blend composition on the mechanical properties, morphological structure, and thermal behavior of PP/EPDM blends were investigated. The results showed that after photocrosslinking, tensile strength, modulus of elasticity, and elongation at break were improved greatly. Moreover, the notched Izod impact strength was obviously enhanced compared with corresponding uncrosslinked blend. Scanning electron microscopy (SEM) morphological analysis showed that for uncrosslinked PP/EPDM blends, the cavitation of EPDM particles was the main toughening mechanism; whereas for dynamically photocrosslinked blends, shear yielding of matrix became the main energy absorption mechanism. The DSC curves showed that for each dynamically photocrosslinked PP/EPDM blend, there was a new smaller melting peak at about 152°C together with a main melting peak at about 166°C. Dynamic mechanical thermal analysis (DMTA) indicated that the compatibility between EPDM and PP was improved by dynamic photocrosslinking. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3371–3380, 2004     

动态硫化PP／EPDM性能对共混工艺的依赖及其机理研究

本文通过对一步法和母料法两种共混工艺制备的动态硫化ＰＰ／ＥＰＤＭ力学性能、拉伸形变特性,熔体流动行为,交联程度和微观结构等的表征和分析,研究了动态硫化ＰＰ／ＥＰＤＭ性能对共混工艺的依赖及其作用机理。结果显示,在保证有效地提高材料加工流动性的前提下,母料法能有效地抑制动态硫化中ＰＰ的降解,提高ＥＰＤＭ的交联程度,粒度均匀性和分散均匀性,从而强化材料的增韧效果以及其它力学性能,并提高材料性能的均匀性。     

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     

Dynamically cured polypropylene/epoxy blends

The dynamic vulcanization process, usually used for the preparation of thermoplastic elastomers, was used to prepare polypropylene (PP)/epoxy blends. The blends had crosslinked epoxy resin particles finely dispersed in the PP matrix, and they were called dynamically cured PP/epoxy blends. Maleic anhydride grafted polypropylene (MAH‐g‐PP) was used as a compatibilizer. The effects of the reactive compatibilization and dynamic cure were studied with rheometry, capillary rheometry, and scanning electron microscopy (SEM). The crystallization behavior and mechanical properties of PP/epoxy, PP/MAH‐g‐PP/epoxy, and dynamically cured PP/epoxy blends were also investigated. The increase in the torque at equilibrium for the PP/MAH‐g‐PP/epoxy blends indicated the reaction between maleic anhydride groups of MAH‐g‐PP and the epoxy resin. The torque at equilibrium of the dynamically cured PP/epoxy blends increased with increasing epoxy resin content. Capillary rheological measurements also showed that the addition of MAH‐g‐PP or an increasing epoxy resin content increased the viscosity of PP/epoxy blends. SEM micrographs indicated that the PP/epoxy blends compatibilized with PP/MAH‐g‐PP had finer domains and more obscure boundaries than the PP/epoxy blends. A shift of the crystallization peak to a higher temperature for all the PP/epoxy blends indicated that uncured and cured epoxy resin particles in the blends could act as effective nucleating agents. The spherulites of pure PP were larger than those of PP in the PP/epoxy, PP/MAH‐g‐PP/epoxy, and dynamically cured PP/epoxy blends, as measured by polarized optical microscopy. The dynamically cured PP/epoxy blends had better mechanical properties than the PP/epoxy and PP/MAH‐g‐PP/epoxy blends. With increasing epoxy resin content, the flexural modulus of all the blends increased significantly, and the impact strength and tensile strength increased slightly, whereas the elongation at break decreased dramatically. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1437–1448, 2004     

Mechanical,thermal, and morphological characteristics of compatibilized and dynamically vulcanized polyoxymethylene/ethylene propylene diene terpolymer blends

Dynamically vulcanized blends of polyoxymethylene (POM) and ethylene propylene diene terpolymer (EPDM) with and without compatibilizer were prepared by melt mixing in a twin screw extruder. Maleic anhydride (MAH) grafted EPDM (EPDM‐g‐MAH) has been used as a compatibilizer. Dicumyl peroxide was used for vulcanizing the elastomer phase in the blends. Mechanical, dynamical mechanical, thermal, and morphological properties of the blend systems have been investigated as a function of blend composition and compatibilizer content. The impact strength of both dynamically vulcanized blends and compatibilized/dynamically vulcanized blends increases with increase in elastomer content with decrease in tensile strength. Dynamic mechanical analysis shows decrease in tanδ values as the elastomer and compatibilizer content increased. Thermograms obtained from differential scanning calorimetric studies reveal that compatibilized blends have lower T_m values compared to dynamically vulcanized blends, which confirms strong interaction between the plastic and elastomer phase. Scanning electron microscopic observations on impact fractured surface indicate reduction in particle size of elastomer phase and its high level of dispersion in the POM matrix. In the case of compatibilized blends high degree of interaction between the component polymers has been observed. POLYM. ENG. SCI., 47:934–942, 2007. © 2007 Society of Plastics Engineers     

Effect of dynamic cross‐linking on melt rheological properties of polypropylene/ethylene‐propylene‐diene rubber blends

Study of melts rheological properties of unvulcanized and dynamically vulcanized polypropylene (PP)/ethylene‐propylene‐diene rubber (EPDM) blends, at blending ratios 10–40 wt %, EPDM, are reported. Blends were prepared by melt mixing in an internal mixer at 190°C and rheological parameters have been evaluated at 220°C by single screw capillary rheometer. Vulcanization was performed with dimethylol phenolic resin. The effects of (i) blend composition; (ii) shear rate or shear stress on melt viscosity; (iii) shear sensitivity and flow characteristics at processing shear; (iv) melt elasticity of the extrudate; and (v) dynamic cross‐linking effect on the processing characteristics of the blends were studied. The melt viscosity increases with increasing EPDM concentration and decreased with increasing intensity of the shear mixing for all compositions. In comparison to the unvulcanized blends, dynamically vulcanized blends display highly pseudoplastic behavior provides unique processing characteristics that enable to perform well in both injection molding and extusion. The high viscosity at low shear rate provides the integrity of the extrudate during extrusion, and the low viscosity at high shear rate enables low injection pressure and less injection time. The low die‐swell characteristics of vulcanizate blends also give high precision for dimensional control during extrusion. The property differences for vulcanizate blends have also been explained in the light of differences in the morphology developed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1488–1505, 2000     

Studies on mechanical and morphological behavior of hybrid nanoclay‐reinforced EPDM‐g‐TMEVS/PS blends

A new copolymer of tris(2‐methoxyethoxy) vinylsilane (TMEVS)‐grafted ethylene–propylene–diene elastomer (EPDM‐g‐TMEVS) has been developed by grafting of TMEVS onto EPDM by using dicumylperoxide (DCP) initiator. The linear polystyrene blends (EPDM‐g‐TMEVS/PS) based on EPDM‐g‐TMEVS have been synthesized with varying weight percentages of polystyrene in a twin‐screw extruder. In a similar manner, the dynamically vulcanized and nanoclay‐reinforced polystyrene blends have also been developed using DCP and organically modified montmorillonite clay separately by means of a twin‐screw extruder. The grafting of TMEVS onto EPDM at allylic position present in the third monomer of EPDM has been confirmed by Fourier Transform infrared spectroscopy. The effect of silane‐grafted EPDM and concentration of nanoclay on mechanical properties of polystyrene blends has been studied as per ASTM standards. The morphological behavior of these blends has been investigated using scanning electron microscope. It was observed that the incorporation of silane‐grafted EPDM enhanced the impact strength and the percentage elongation of linear‐ and dynamically vulcanized blends. However, the values of tensile strength, flexural strength, flexural modulus, and hardness of the blends were found to be decreasing with the increase of silane‐grafted EPDM. In the case of nanoclay‐reinforced polystyrene blends, the values of impact strength, tensile strength, flexural strength, flexural modulus, and hardness were increased with an increase in the concentration of nanoclay. XRD studies have been carried out to confirm the formation of nanoclay‐reinforced EPDM‐g‐TMEVS/PS blends. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

Morphology development of EPDM/PP uncross‐linked/dynamically cross‐linked blends

Ethylene‐propylene‐diene‐terpolymer (EPDM) and polypropylene (PP)‐based uncross‐linked and dynamically cross‐linked blends were prepared both in an internal mixer and in a corotating twin‐screw extruder. The effects of composition, plasticization and mixing equipment on the morphology development and the final viscoelastic properties were studied. In the uncross‐linked blends, the plasticization resulted in a coarser morphology. Furthermore, it was shown that the majority of the plasticizer resided in the EPDM phase, enabling its deformation in the flow direction. In addition, the intensive mixing conditions inside the twin‐screw extruder resulted in a finer morphology. In the dynamically cross‐linked blends, the twin‐screw extrusion process resulted in a higher level of gel content with larger EPDM domains. The plasticization showed again a coarsening effect, resulting in interconnected cross‐linked EPDM domains. An interesting interfacial phenomenon was observed especially in the plasticized vulcanized blends where nanometer size occluded PP domains were stripped off and eroded into the EPDM phase. With the exception of the nonplasticized uncross‐linked blends, the viscoelastic properties of all other blending systems were found to be directly affected by the morphology, gel content (in the case of cross‐linked blends), and the presence of the plasticizer. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

In situ compatibilization of polypropylene/polystyrene blend by controlled degradation and reactive extrusion

In situ compatibilization of polypropylene (PP) and polystyrene (PS) was achieved by combinative application of tetraethyl thiuram disulfide (TETD) as degradation inhibitor and di‐tert‐butyl peroxide as degradation initiator in the process of reactive extrusion. The PP/PS blends obtained were systematically investigated by rheological measurement, scanning electron microscopy, and differential scanning calorimetry. The results indicate that peroxide‐induced degradation of PP can be effectively depressed by adding TETD, which may favor the formation of PP‐g‐PS copolymer during melt processing. The PP‐g‐PS copolymer formed may act as an in situ compatibilizer for PP/PS blends, and subsequently decreases the size of dispersed PS phase and changes both rheological and thermal properties of the blends. Based on the present experimental results, the mechanisms for the controlled degradation of PP and in situ formation of PP‐g‐PS copolymer in the PP/PS blends have been proposed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009