Rheological properties and crystalline structure of the dynamically cured EPDM and PP/HDPE ternary blends

The rheological properties and crystalline structure of the polyolefin ternary blends of EPDM/polypropylene/high density polyethylene were studied. Blends were prepared in a laboratory internal mixer by two different methods. In blend–cure process, blending and curing were performed simultaneously and EPDM was cured by dicumyl peroxide (DCP) in the presence of PP/HDPE under shear. The cure–blend was to cure EPDM alone first under shear (dynamic curing) and then mix the cured EPDM with PP and HDPE. The effect of DCP concentration, intensity of the shear mixing, and the rubber/plastic composition were studied using capillary rheometer and X-ray diffractometer. The PP-rich ternary blends showed the effect of the mechanooxidative degradation of PP by shear and peroxide. The melt viscosity increased with increasing DCP concentration in blends of EPDM-rich compositions. X-ray diffraction studies revealed that the inclusion of 25 wt % of linear EPDM in the PP/HDPE mixture for the PP-rich ternary blends changed the crystal structure of polypropylene component in the ternary blends. However, the dynamic curing did not alter the crystal structure of PP or HDPE in the blends.     

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.     

硫化体系对EPDM／ACM共混胶性能的影响

研究了7种不同硫化体系对EPDM／ACM共混胶性能的影响。结果表明,采用DCP／TCY硫化体系硫化的共混胶,具有合适的正硫化时间和交联密度,拉伸强度接近最大值,为17．2MPa,撕裂强度最大,为38．5N／mm,压缩永久变形最小,为30．6％,耐热空气老化性能较好。DCP／TCY并用硫化体系为EPDM／ACM共混胶的最佳硫化体系。     

Thermoplastic elastomers based on high‐density polyethylene,ethylene–propylene–diene terpolymer,and ground tire rubber dynamically vulcanized with dicumyl peroxide

Thermoplastic vulcanizates (TPVs) based on high‐density polyethylene (HDPE), ethylene–propylene–diene terpolymer (EPDM), and ground tire rubber (GTR) were dynamically vulcanized with dicumyl peroxide (DCP). The polymer blend was composed of 40% HDPE, 30% EPDM, and 30% GTR, and the concentration of DCP was varied from 0.3 to 3.6 parts per hundred rubber (phr). The properties of the TPVs were determined by evaluation of the gel fraction content and the mechanical properties. In addition, IR spectroscopy and differential scanning calorimetry analysis were performed as a function of the DCP content. Decreases in the Young's modulus of the blends and the crystallinity of HDPE were observed when the content of DCP was greater than 1.8 phr. The results regarding the gel content indicate that the presence of DCP promoted the crosslinking of the thermoplastic matrix, and optimal properties were obtained with 1.5% DCP. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39901.     

Application of phase dispersion–crosslinking synergism on recycling commingled plastic wastes

A tetra‐component blend, consisting of low‐density polyethylene (LDPE), polyvinyl chloride (PVC), polypropylene (PP), and polystyrene (PS), was studied as a model system of commingled plastic wastes (LDPE/PVC/PP/PS, mass ratio: 70/10/10/10). Effects of chlorinated polyethylene (CPE), ethylene–propylene–diene monomer (EPDM), styrene–butadiene–styrene (SBS), and their mixture (CPE/EPDM/SBS, mass ratio: 2/2/2) on the mechanical properties and morphology of the system were investigated. With addition of several elastomers and their mixture, the tensile strength of the blends decreased slightly, although both the elongation at break and the impact strength increased. Among these elastomers, EPDM exhibited the most significant impact modification effect for the tetra‐component blends. SBS and the mixture have a good phase‐dispersion effect for the tetra‐component blend. By adding a crosslinking agent [dicumyl peroxide (DCP)], the mechanical properties of the tetra‐component blends also increased. When either SBS or the mixture was added to the blend together with DCP, the probability that the crosslinking agent (DCP) would be at the interface improved because of the phase‐dispersion effect of SBS. Therefore, more co‐crosslinked products will form between LDPE and other components. Accordingly, remarkable improvement of the interfacial adhesion and hence the mechanical properties of the tetra‐component blends occurred. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2947–2952, 2001     

1,2-PBR和BR对EPDM硫化和力学性能的影响

考察了过氧化物硫化体系和硫黄硫化体系ＥＰＤＭ／１,２－聚丁二烯橡胶（１,２－ＰＢＲ）和ＥＰＤＭ／ＢＲ并用胶的硫化特性、交联密度和物理性质。结果表明：采用过氧化物硫化体系时,ＥＰＤＭ与１,２－ＰＢＲ和ＢＲ并用后,硫化胶的交联密度、１００％定伸应力、邵尔Ａ型硬度和撕裂强度增大,且前的增幅较大;采用硫黄硫化体系时,１,２－ＰＢＲ和ＢＲ均可提高ＥＰＤＭ的硫化速率,且随着１,２－ＰＢＲ用量的增大,硫化胶的     

Dynamic vulcanization of polyethylene‐based thermoplastic elastomer blends

In this investigation, the effects of blending with ethylene–propylene–diene terpolymer and subsequent dynamic curing with sulfur on the macromolecular structure and properties of pure low‐density polyethylene and high‐density polyethylene were studied. The crosslinking efficiency of polyethylene‐based ethylene–propylene–diene terpolymer blends upon dynamic curing was assessed with torque and gel content measurements. The curing of dispersed ethylene–propylene–diene terpolymer in a polyethylene matrix improved both the mechanical and thermomechanical properties as a result of the formation of a crosslink structure in the rubber phase. In view of the electrical applications of this cured blend material, the volume resistivity was measured. The thermal stability of vulcanized polyethylene/ethylene–propylene–diene terpolymer blends was found to be superior to that of unvulcanized blends. In scanning electron microscopy analysis, good interface bonding between the polyethylene matrix and dispersed ethylene–propylene–diene terpolymer was observed for the cured blends. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Crosslinking of polypropylene–polyethylene blends by peroxide and the effect of pentaerythritol tetrallyl ether

Crosslinking of polypropylene–polyethylene (PP-PE) blends involving 10, 20, 30, 40, 50, 60, 70, 80, and 90% of PP with dicumylperoxide (DCP) or tert-butyl perbenzoate (TBPB) and in the presence of coagent pentaerythritol tetrallyl ether (PETA) was investigated at 180°C. It was found that at lower concentrations of peroxide alone (e.g., 2.5% of DCP) only PE component is crosslinked in all compositions of PP-PE blends. In the crosslinking of PP-PE 50:50 with 4% of TBPB, insoluble gel was obtained, which contained 13% PP and 87% PE. If 2% PETA was also used, the portion of PP in gel increased to 39%; the total yield of gel in PP-PE blend increased from 50 to 70%. The lower crosslinking efficiency of coagent PETA in the PP-PE blends compared with PP alone is associated with better solubility of the coagent in the PE phase in contrast to the PP phase. The coagent does not particularly raise the crosslinking efficiency of peroxide in PE, but increases it in the PP phase. A remarkable decrease in melting temperature and temperature of crystallization of both polymer components depending on peroxide concentration was found by calorimetric measurements.     

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.     

HNBR/EPDM共混物结构与性能研究

分别采用过氧化物和硫给予体作交联剂,考察了不同共混比对氢化丁腈橡胶（ＨＮＢＲ）／ＥＰＤＭ共混物性能的影响,并能力ＤＳＣ和ＴＥＭ分析了共混物的相容性,对两胶的共硫化也作了初步探讨。结果表明,两种硫化体系硫化的共混胶扯断伸长率保持率均在６０％以上,都具有优异的耐热氧老化性能。随ＨＮＢＲ用量增大,共混物的定伸应力、拉伸强度和撕裂强度均提高,磨耗明显降低。ＨＮＢＲ和ＥＰＤＭ为不相容体系,但硫化仪曲线显示二     

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.     

EPDM/NR并用胶的复合交联

采用硫黄硫化体系和过氧化物（硫化剂DCP）硫化体系对EPDM／NR并用胶实施复合交联，研究并用比和复合交联体系对胶料的硫化特性、物理性能和耐热老化性能的影响。结果表明，在大部分并用比下，复合交联可以改善胶料的硫化特性；在硫化剂DCP和助交联剂TAIC的用量均为2份、EPDM／NR／ENR并用比为30／68．5／1．5时，并用胶的物理性能优良；以NR为主的并用胶在复合交联时硫化剂DCP和助交联剂TAIC的用量宜取1～2份。     

Structure and properties of dynamically cured EPDM/PP blends

The structure and properties of polyolefin blends of ethylene–propylene–diene terpolymer (EPDM) and polypropylene were studied. Blends were prepared in a laboratory internal mixer where EPDM was cured with PP under shear with dicumyl peroxide (DCP) at different shear conditions (blend–cure). Blends were also prepared for comparison from EPDM which were dynamically cured in the absence of PP and blended later (cure–blend). The effect of DCP concentration, intensity of the shear mixing, and rubber/plastic composition were studied. In blend–cure, the melt viscosity increased with increasing DCP concentration in blends of 75% EPDM and 25% PP, but it decreased with increasing DCP concentration in blends of 75% PP and 25% EPDM. In cure–blend, however, the melt viscosity increased with increasing DCP concentration for all compositions. The melt viscosity decreased with increasing intensity of the shear mixing presumably due to the formation of the smaller segregated microdomain of the crosslinked EPDM gels in both blend–cure and cure–blend materials. The crystallization rate was higher in EPDM/PP blends than in PP homopolymer. The crystallization rates for various blending conditions were also compared.     

助交联剂PDM和硫黄用量对CM/EPDM并用胶性能的影响

试验研究在过氧化物硫化体系下助交联剂N,N'-间亚苯基双马来酰亚胺(PDM)和硫黄用量对氯化聚乙烯橡胶(CM)/EPDM并用胶性能的影响.结果表明:在硫化剂DCP/助交联剂PDM硫化体系下,当硫化剂DCP用量为3份、助交联剂PDM用量为1.5～2份时,CM/EPDM并用胶的综合性能较好;在硫化剂DCP/硫黄硫化体系下,...     

Development of polybutadiene (BR)–polyethylene (LDPE) blend based microcellular soles for low‐temperature applications

Microcellular (MC) soles based on polybutadiene (BR) and low‐density polyethylene (LDPE) blends for low‐temperature applications were developed. A part of BR in BR–LDPE blend was replaced by natural rubber (NR) for property improvement. The BR–NR–LDPE blend‐based MC sole shows good technical properties. Sulphur curing and DCP curing were tried in BR–LDPE and NR–BR–LDPE blends. Study shows that sulphur‐cured MC sheets possess better technical properties than DCP‐cured MC sheets. 90/10 BR–LDPE and 60/30/10 BR–NR–LDPE blend combinations are found to be suitable for low‐temperature applications. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 277–281, 2000     

动态硫化PP／HDPE／EPDM三元共混物的流变性能

本文采用不同的硫化剂，不同的硫化时间，对动态硫化的ＰＰ／ＨＤＰＥ／ＥＰＤＭ三元共混物的流变性能进行了研究。结果表明：１共混体系为假塑体，表现出切力变稀现象；２在低剪切应力下，以Ｍ为硫化剂的粘度与纯机械共混体系的粘度有很大差值，此差值随剪切应力的提高迅速减少；３以ＤＣＰ为硫化剂，体系的粘度低于纯机械共混体系的粘度。     

化学交联PE-LD/SBS共混物的形状记忆效应研究

分别用3种不同苯乙烯含量的苯乙烯-丁二烯共聚物(SBS)与低密度聚乙烯(PE-LD)混合制成共混物,采用过氧化苯甲酰(BPO)为引发剂,使共混物发生化学交联形成网状结构,对交联共混物的交联度进行了分析,测试了交联共混物的拉伸强度与断裂伸长率,探讨了交联共混物的形状记忆效应。结果表明,在PE-LD/SBS共混物中,随着BPO含量的增加,共混物的交联度增大;BPO含量固定时,随着SBS中丁二烯含量的增大共混物的交联度增大;随着交联度的增加,共混物的拉伸强度与断裂伸长率均下降;当BPO含量为0.5 %～1.5 %时,交联共混物具有良好的形状记忆效应。     

Effect of blend ratio on cure characteristics,tensile properties,thermal and swelling properties of mica‐filled (ethylene‐propylene‐diene monomer)/(recycled ethylene‐propylene‐diene monomer) (EPDM/r‐EPDM) blends

(Ethylene‐propylene‐diene monomer)/(recycled ethylene‐propylene‐diene monomer) (EPDM/r‐EPDM) blends filled with constant mica loading were compounded at various blends ratios (i.e., 90/10, 80/20, 70/30, 60/40, and 50/50). Results indicated that scorch time decreased with increasing r‐EPDM content, whereas curing time, minimum torque, and maximum torque show the opposite trend. The tensile strength, stress at 100% elongation, and elongation at break value increased with increasing r‐EPDM loading in the blend systems and the optimum properties occurred at 70/30 EPDM/r‐EPDM blends ratio. The thermal stability of EPDM/r‐EPDM blends increased with increasing r‐EPDM content in the blends but the swelling percentage showed the opposite trend with a greater addition of r‐EPDM content in the blends. J. VINYL ADDIT. TECHNOL., 21:1–6, 2015. © 2014 Society of Plastics Engineers     

Thermal characteristics and temperature profile changes of structurally different polyethylenes with peroxide modifications

Crosslinking and processing characteristics of polyethylenes (PEs) with different molecular architectures, namely high‐density polyethylene (HDPE), linear low‐density polyethylene (LLDPE), and low‐density polyethylene (LDPE), were studied with regard to the effects of peroxide modifications and coolant flow rates. Dicumyl peroxide (DCP) and di‐tert‐butyl peroxide (DTBP) were used as free‐radical inducers for crosslinking the PEs. The characteristics of interest included normalized gel content, real‐time temperature profiles and their cooling rates, exothermic period, crystallinity level, crystallization temperature, and heat distortion temperature. The experiments showed that LDPE exhibited the highest normalized gel content. The real‐time cooling rates, taken from the temperature profiles for all PEs before the crystallization region, were greater than those after the crystallization region. The cooling rate of the PEs increased with the presence of DCP, whereas the crystallization temperature of the PEs was lowered. The HDPE appeared to show the longest exothermic period as compared with those of the LLDPE and LDPE. The exothermic period showed an increase with increasing coolant flow rate, but it was decreased by the use of DCP. As for the effect of peroxide type, the gel content and cooling rate of the PE crosslinked by DCP were higher than those for the PE crosslinked by DTBP. The DTBP was the more effective peroxide for introducing crosslinks and simultaneously maintaining the crystallization behavior of the PE. J. VINYL ADDIT. TECHNOL., 20:80‐90, 2014. © 2014 Society of Plastics Engineers     

EPDM硫化橡胶的热稳定性研究

对ＥＰＤＭ的过氧化物硫化、硫黄硫化和含硫化合物硫化以及两种不同硫化体系并用的硫化胶热稳定性进行比较，优选热稳定性较好的硫化体系用于产品的制造。采用过氧化二异丙苯（ＤＣＰ）硫化的硫化胶虽具有极好的热稳定性，但其耐撕裂性能较差，且价格较高。因此可考虑采用ＤＣＰ的并用硫化体系。当ＤＣＰ用量为５份，硫黄用量不超过１份时，硫化胶具有较好的热稳定性。