Dynamic Vulcanization of Thermoplastic Elastomers Based on Poly(Epichlorohydrin-Co-Ethylene Oxide) and Polypropylene

Summary Unvulcanized and dynamically vulcanized blends of poly(epichlorohydrin-co-ethylene oxide) elastomer and polypropylene have been prepared by melt mixing in an internal mixer. The solvent resistance, morphology, dynamic mechanical and mechanical properties of these blends were studied with special reference to the effect of the crosslinking agent content. The swelling behaviour shows that the blends, with and without dynamic vulcanization, present excellent resistance to solvents ASTM A, B, C and D, at room temperature. Morphology study by scanning electron microscopy of the cryofractured surface and analysis of the dynamic mechanical properties of the system indicate that the uncrosslinked blend is immiscible and form a two-phase structure, where the rubber phase was dispersed as domains in the continuous polypropylene matrix. The mechanical properties of the crosslinked blends do not improve by increasing the doses of crosslinking agent.     

Phase morphology and melt rheological behavior of uncrosslinked and dynamically crosslinked polyolefin blends: role of macromolecular structure

Thermoplastic vulcanizates (TPVs) based on polypropylene (PP) with ethylene–octene copolymer (EOC) and ethylene propylene diene rubber (EPDM) have been prepared by co-agent-assisted peroxide crosslinking system. The study was pursued to explore the influence of two dissimilar polyolefin polymers having different molecular architecture on the state and mode of dispersion of the blend components and their influence on melt rheological properties. The effects of dynamic crosslinking of the PP/EOC and PP/EPDM have been compared with special reference to the concentration of crosslinking agent and ratio of blend components. Morphological analyses show that, irrespective of blend ratio, dynamic vulcanization exhibits a dispersed phase morphology with crosslinked EOC or EPDM particles in the continuous PP matrix. It was found that viscosity ratio plays a crucial role in determining the state and mode of dispersion of blend components in the uncrosslinked system. The lower viscosity and torque values of uncrosslinked and dynamically crosslinked blends of PP/EOC in the melt state indicates that they exhibit better processing characteristics when compared to corresponding PP/EPDM blends.     

动态交联PP/EVA共混物的制备与性能研究

本文将动态交联技术应用于PP/EVA共混体系中,制得动态交联PP/EVA共混物。采用Hakke转矩流变仪研究了动态交联对PP/EVA共混物扭矩的影响;研究了DCP和EVA含量对共混物力学性能的影响;考察了动态交联共混物的维卡软化点。结果表明：加入DCP后,PP/EVA共混物扭矩先升后降,DCP的添加量为EVA含量的1%为宜。随EVA用量的增加,动态交联EVA/PP共混物的冲击强度大幅提高,但拉伸强度有所降低。少量经动态交联的EVA颗粒可以促进共混物中PP的结晶, 提高共混物的维卡软化点。     

Rubber phase dispersion in polypropylene

Impact properties of rubber-modified blends are significantly dependent on particle size and size distribution (dispersion). Past work has shown strong variations in these particle parameters with different processing conditions and these variations reflect, in part, different shear fields developed during melt extrusion and moulding. A major problem ensues involving property variability because of process variability. It is neither practical nor economical to place stringent controls on process variability in a plant. Instead, our current research has indicated that lightly crosslinking the rubber reduced drastically the sensitivity of dispersion to processing conditions, and, with the correct rheology between the rubber and the resin, the same dispersion could be maintained through both the extrusion and moulding stages resulting in finished parts with increased chance of dispersion and property consistency. Four rubbers of different degrees of crosslinking and three polypropylenes of different melt flow and structure were blended at six rubber levels. Mixing was carried out with two twin-screw configurations and the blends were cast or injection moulded using a ram or a screw moulder representing six different processing shear histories. Dispersion was quantitatively characterized by scanning electron microscopy (SEM). Spherical rubber particles revealed on the fracture surface were counted and measured to determine particle size and size distribution for the individual blends. Correlation of the results indicated how particle size and size distribution was influenced by crosslinking and the rubber/resin rheology. This provided some understanding of the mechanics of soft-phase dispersion in these blends.     

Comprehensively improved mechanical properties of silane crosslinked polypropylene/ethylene propylene diene monomer elastomer blends

The properties and structure of silane crosslinked polypropylene (PP)/ethylene propylene diene monomer (EPDM) elastomer blends had been carried out. Fourier transform infrared spectroscopy and gel content tests were employed to evaluate the crosslinking reaction of PP/EPDM blends. Crosslinking efficiency of PP/EPDM blends was investigated using thermogravimetric analysis, differential scanning calorimeter, dynamic mechanical analysis, dynamic rheology, and tensile testing. Tanδ curves of silane crosslinked PP/EPDM blends exhibited an obvious “gel point” originated from the formation of dynamic crosslinking network. The blend corresponding to the “gel point” presented comprehensively improved mechanical properties. These results demonstrated that characteristic rheological parameters showed close correlations with key mechanical properties of silane crosslinked PP/EPDM blends. Scanning electron microscopy images illustrated that crosslinking had remarkably changed the morphologies of PP/EPDM blends. The large deformation mechanism of these blends had been suggested.     

Morphology development by reactive compatibilisation and dynamic vulcanisation of nylon6/EPDM blends with a high rubber fraction

Binary nylon6/rubber blends with 50 or 60 weight percent of an EPDM rubber exhibit co-continuous morphologies and thereby relatively poor mechanical properties. This paper describes methods to develop nylon6/EPDM blends with a high amount of finely dispersed rubber particles embedded in a nylon matrix. Using a suitable compatibiliser and by slightly crosslinking the rubber phase during melt-mixing, it was possible to disperse up to 60 wt% rubber in the nylon matrix and to improve the mechanical properties markedly. These materials are called thermoplastic vulcanisates and exhibit good elastic properties with a thermoplastic processability. The influence of the compatibiliser, the crosslinking agent and the viscosity ratio rubber/thermoplastic on the blend phase morphology is investigated using transmission electron microscopy. It was found that the viscosity ratio rubber/nylon plays a crucial role in order to achieve a nylon6/rubber TPV with a fine rubber dispersion. The viscosity of the nylon phase should be low enough to shift the phase inversion towards higher rubber content. On the other hand, if the viscosity of the nylon is too low, a coarse blend morphology was achieved resulting in poor mechanical properties.     

Structure and properties of polyolefin blends

Blends of ethylene–propylene–diene rubber (EPDM) and low density polyethylene (PE_id) or isotactic polypropylene (iPP) crosslinked by dicumyl peroxide (DCP) have been prepared. Their morphology, reactivity of the components and crystallinity have been studied. The blends are microheterogeneous. Both plastomers, but particularly iPP, decrease the crosslinking efficiency of EPDM by DCP. It was found that they also influence the mechanical properties of the blends. The effect of iPP is far more pronounced than that of PE_Id, because of an increase in crystalline phase content. iPP particles play a role as nuclei for propylene monomer units in EPDM, whereas PE_Id particles are solvated by the elastomer matrix.     

炭黑对动态硫化POE/PP热塑性弹性体性能的影响

采用动态硫化法制备POE/PP共混物,研究了过氧化二异丙苯（DCP）对POE/PP体系熔体流动速率（MFR）和力学性能的影响。交联助剂硫磺（S）的加入有效地提高了交联效果,当m（DCP）/m（S）=2/0.2时,体系的综合力学性能最佳。通过不同加工工艺制备POE/PP/炭黑共混物,并研究了炭黑用量对体系力学性能和老化性能的影响。结果表明,母料法制备的共混物更有利于炭黑的分散,体系性能更好,炭黑的加入使体系的耐热老化性和抗紫外性能明显改善。     

Thermal Stability and Crystallization Behavior of TER Blends of Isotactic Polypropylene (iPP)/Ethylene-Propylene Diene Rubber (EPDM)/Nitrile Rubber (NBR)

The blends of isotatic polypropylene (iPP), ethylene-propylene diene rubber (EPDM), and nitrite rubber (NBR) were prepared using dimethylol phenolic resin as a crosslinking system. The dynamically crosslinked blends of iPP/EPDM/NBR showed superior thermal stability to that of virgin isotactic polypropylene (iPP). Dynamic crosslinking rendered the vulcanizate thermally more stable as compared to uncrosslinked blends, which can be attributed due to the variations in degree of crosslinking and degree of crystallinity.

Crystallization of iPP in the blends of iPP/EPDM/NBR was also studied through Temperature Modulated Differential Scanning Calorimetry (TMDSC). Other detailed analysis of endotherm peaks obtained after first and second melts in terms of heat of enthalpy, degree of undercooling, and degree of crystallinity were also evaluated. Various kinetic parameters were also determined. Degree of crosslinking increases the interfacial adhesion between the iPP and EPDM/NBR phases. Dimethylol phenolic resin used as a compatibilizer also enhanced the thermal stability of the iPP/EPDM/NBR blends.     

Effect of crosslinking on polyamide 11/butadiene-acrylonitrile copolymer blends

The effect of crosslinking of polyamide 11 and butadiene-acrylonitrile copolymer (nitrile rubber) was studied. The effect of static and dynamic crosslinking on blending are described. Static and dynamic crosslinking do not significantly improve impact strength of low-rubber-content PA11/NBR blends. For blends with dynamic crosslinking and high rubber contents, mechanical properties including impact strength improve. Thermal behavior of crosslinked PA11/NBR blends were studied by DSC and DMA. SEM was used for investigation of the effect of crosslinking on particle size and particle size distribution, phase morphology, and fracture surface morphology. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1605–1611, 1997     

PP／废旧橡胶／SBS复合材料的制备和力学性能研究

通过磨盘型力化学反应器制备PP/废旧橡胶(WTR)复合粉体，然后与SKS共混制备PP/WTR/SBS复合材料。研究了材料的力学性能、微观结构和共混物的加工性质。结果表明：当SBS添加量在20％～25％时，PP/WTR/SBS复合材料的力学性能较PP/WTR有了很大的提高，当SBS用量为25％时，断裂伸长率提高了365％，冲击强度提高了73．2％，而体系的拉伸强度基本不变。复合材料冲击断面的形貌和复合体系流变性能研究结果表明：磨盘碾磨可有效改善各组分间的混合性能，提高相容性并有效改善材料的加工性能。     

Evolution of rheological properties and morphology development during crosslinking of polyolefin elastomers and their TPV blends with polypropylene

This work investigates the evolution of the rheological properties of elastomeric dynamically vulcanized ethylene‐α‐olefin copolymers (ECs) and their blends with polypropylene (PP), during peroxide initiated crosslinking. Rheological techniques are used in conjunction with gel content measurements to determine the onset of gelation during static crosslinking. The complex viscosity and moduli follow power‐law dependence with respect to frequency at the gel point. The relaxation exponent and corresponding values of tan δ at the gel point are determined from the complex viscosity versus frequency curves and used as criteria for the determination of the instance of gelation. The evolution of morphology of thermoplastic vulcanizate (TPV) blends consisting of EC and PP during dynamic crosslinking is discussed in the context of the evolving rheological properties of the matrix and the dispersed phase that take place upon peroxide modification. TPVs having the crosslinked EC as the matrix present a very fine morphology, whereas the blends containing crosslinked EC particles, present a coarser morphology. POLYM. ENG. SCI., 2009. © 2008 Society of Plastics Engineers     

乙烯基含量对热硫化硅橡胶抗撕裂性能的影响

研究不同乙烯基含量对热硫化硅橡胶的力学性能尤其是抗撕裂性能的影响,采用平衡溶胀法测定硅橡胶的交联密度,研究不同乙烯基含量的硅橡胶并用胶的撕裂强度和交联密度的关系。结果表明,随着硅橡胶乙烯基含量的增大,硅橡胶硫化胶的断裂伸长率减小,300%定伸应力和硬度升高,当乙烯基摩尔分数为0.15%时,撕裂强度和拉伸强度较高。乙烯基摩尔分数为0.15%的硅橡胶和乙烯基摩尔分数为0.06%的硅橡胶并用,当并用比为50/50时,撕裂强度高达45.8 kN/m,乙烯基摩尔分数为0.30%的硅橡胶和乙烯基摩尔分数为0.06%的硅橡胶并用,当并用比为4/96时,撕裂强度可达42.9kN/m。乙烯基摩尔分数为0.30%的硅橡胶和乙烯基摩尔分数为0.15%的硅橡胶并用,并用比对硫化胶的撕裂强度影响不大。高乙烯基含量和低乙烯基含量的硅橡胶并用,有利于使硅橡胶的交联结构由"分散交联"转变为"集中交联",当并用胶的乙烯基摩尔分数在0.15%以内,硅橡胶并用胶的撕裂强度随乙烯基摩尔分数的增加而先增大后降低,而此时并用胶的交联密度与撕裂强度成反比。     

LLDPE/POE共混物的交联行为研究

采用过氧化物交联研究了线性低密度聚乙烯(LLDPE)/乙烯-α-辛烯共聚物(POE)共混物。研究了工艺、配方对LLDPE/POE共混物凝胶含量的影响,以及凝胶含量与材料力学性能的关系。结果表明,LLDPE/POE共混物的凝胶含量随引发剂的用量、交联温度和交联时间的增加而增加,达到一定程度后不再增加。在170℃,30min的条件下DCP能充分分解引发交联反应,DCP用量为1.5%时,共混物的凝胶含量可以达到80%以上,再增加时凝胶含量不再增加。DCP的加入顺序对共混物的凝胶含量影响不大。共混物的凝胶含量对其动态力学行为有影响。共混物的凝胶含量对拉伸性能影响不大。     

Mechanical Properties and Morphology of Nitrile Rubber Toughened Polystyrene

Mechanical properties and morphology of blends of polystyrene and finely powdered (uncrosslinked and crosslinked) nitrile rubber were studied with special reference to the effect of blend ratio. Blends were prepared by melt mixing polystyrene and nitrile rubber in an internal mixer at 180°C in the composition range of 0–20 wt% nitrile rubber. The tensile stress/strain properties and impact strength of the polystyrene/nitrile rubber blends were determined using injection molded test specimens. In comparison to the blends with uncrosslinked nitrile rubber, blends with crosslinked nitrile rubber showed higher tensile strength, elongation at break, Young's modulus, impact strength, flexural strength, and flexural modulus. The enhanced adhesion between the dispersed nitrile rubber phase and the polystyrene matrix results in an increase in mechanical properties. Scanning electron micrographs of the fractured surfaces confirm the enhancement in mechanical properties.     

Dynamic mechanical properties of styrene butadiene rubber and poly (ethylene-co-vinyl acetate) blends

The dynamic mechanical behaviour of uncrosslinked and crosslinked styrene butadiene rubber/poly (ethylene-co-vinyl acetate) (SBR/EVA) blends was studied with reference to the effects of blend ratio, crosslinking systems, a compatibilizer viz. maleic-anhydride grafted poly [styrene-b-(ethylene-co-butylene)-b-styrene] (SEBS-g-MA), frequency and temperature. The two separate tan δ peaks, obtained during DMA, indicated the immiscibility of SBR/EVA system. The damping properties increased with SBR content for uncrosslinked and crosslinked blends. In the case of crosslinked systems, depending upon the type of crosslinking agent used, the glass transition temperature (T _g) of SBR phase has been found to be shifted to higher temperatures. The damping characteristics of the blends were observed to be affected by the variations in frequency. The addition of the compatibilizer improved the storage modulus and reduced the damping properties. These results have been correlated with the morphology of the blends, attested by scanning electron micrographs. The activation energy for glass transition has been computed. The experimental data on storage modulus were compared with theoretical predictions.     

Effect of different types of peroxides on properties of vulcanized EPDM + PP blends

Mechanical and tribological behavior of several dynamic vulcanizate blends of polypropylene (PP) with ethylene‐propylene‐diene rubber (EPDM) was examined and compared with those of uncrosslinked blends. Vulcanization was performed using two types of organic peroxides combined with (meth)acrylate coagent. The effect of different types and concentrations of peroxides as crosslinking agents on the properties of the resulting materials were investigated. Dicumyl peroxide (DCP) provides higher reactivity and exhibits nearly the same crosslinking efficiency for both 60/40 and 50/50 blends; almost fully crosslinked samples are obtained if the compound contains 1.0 or 2.0 wt% DCP. These results correlate to the gel content and mechanical properties of our materials. Variation of PP + elastomer ratio does not have a significant influence on friction. From 60/40 group of composites, lower friction values were obtained for samples cured with 0.5 wt% benzoyl peroxide (BP) and 1.0 wt% DCP. The tribological properties of the samples with higher amount of DCP show rubbery rather than a toughened thermoplastic behavior. Wear of the composites decreases with the increasing concentration of the curing agent. Compared to BP, the samples cured with DCP display lower wear. POLYM. COMPOS., 31:1678–1691, 2010. © 2010 Society of Plastics Engineers.     

Radiation preparation of ultrafine carboxylated styrene–butadiene rubber powders and application for nylon 6 as an impact modifier

Ultrafine carboxylated styrene–butadiene rubber(CSBR) powders were prepared by using gamma irradiation and following spray‐drying method. The influences of dose rate, absorbed dose, and sensitizer content on the crosslinking density of CSBR latices were studied in detail. Then the ultrafine CSBR powders were used to toughen nylon 6. The toughness and thermal properties of nylon 6/CSBR blends were measured by using notched lzod impact test and differential scanning calorimetry and thermogravimetry, respectively. Results showed that the crosslinking density of CSBR increased with increasing of dose and sensitizer content, and it is independent on dose rate. The notched Izod impact strength of nylon 6 under room temperature increased after incorporation of irradiation crosslinked CSBR powders with appropriate crosslinking density. The morphology of higher impact nylon 6/CSBR blends indicated that the finer dispersion existed with dispersed particles of 150‐nm diameter. Fracture morphology of nylon 6/CSBR blend suggested that the shear yielding in matrix is the primary toughening mechanism for nylon 6/CSBR blends. The crystallinity of nylon 6/CSBR blends decreased slightly compared with pure nylon 6, whereas the addition of CSBR powders had little influence on the thermal stability of nylon 6. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3040–3046, 2002     

Tensile properties and morphology of the dynamically cured EPDM and PP/HDPE ternary blends

The tensile properties and morphology of the polyolefin ternary blends of ethylenepropylene–diene terpolymer (EPDM), polypropylene and high density polyethylene were studied. Blends were prepared in a laboratory internal mixer where EPDM was cured in the presence of PP and HDPE under shear with dicumyl peroxide (DCP). For comparison, blends were also prepared from EPDM which was dynamically cured alone and blended with PP and HDPE later (cure–blend). The effect of DCP concentration, intensity of the shear mixing, and rubber/plastics composition was studied. The tensile strength and modulus increased with increasing DCP concentration in the blends of EPDM-rich compositions but decreased with increasing DCP concentration in blends of PP-rich compositions. In the morphological analysis by scanning electron microscopy (SEM), the small amount of EPDM acted as a compatibilizer to HDPE and PP. It was also revealed that the dynamic curing process could reduce the domain size of the crosslinked EPDM phase. When the EPDM forms the matrix, the phase separation effect becomes dominant between the EPDM matrix and PP or HDPE domain due to the crosslinking in the matrix.     

Mechanical and Morphological Properties of PP/LLPDE/NR Blends—Effects of Polyoctenamer

In this study, impact-modified polypropylene (PP) ternary blends based on PP/natural rubber (NR)/linear low-density polyethylene (LLDPE) with ratios of 72/10/18 and 64/20/16 were produced by a twin-screw extruder with polyoctenamer (TOR) as the compatibilizer. The mechanical properties of the blends were determined on injection-molded specimens in tensile, flexural, and impact testing. The impact strength and elongation at break of the blend increased significantly while the flexural modulus and tensile strength decreased slightly with increasing TOR content. The impact strength improved with the increasing TOR due the increase of interfacial adhesion resulting in finer dispersion of the rubbery minor phase in the PP matrix. The improvement in compatibility with the addition of TOR into PP/NR/LLDPE blends is being supported by both scanning electron microscopy (SEM) and dynamic mechanical analysis (DMA).