Characterization of EPDM/atactic polypropylene blends by high-resolution solid-state NMR

The study of EPDM/atactic polypropylene blend compatibility was investigated by cross-polarization/magic angle spinning carbon-13 NMR spectra, variation contact time experiment analysis, proton spin-lattice relaxation time in the rotating frame, carbon-13 spin-lattice relaxation time, and a dipolar dephasing experiment. The data are discussed in terms of mobility and compatibility of polymeric blends. © 1996 John Wiley & Sons, Inc.     

Radiation processing of EPDM/PP blends

The effect of ionizing radiation on thermal oxidation of ethylene-propylene copolymer/polypropylene (EPDM/PP) was evaluated over the range of total gamma doses up to 250 kGy. The influence of irradiation dose on oxidation induction periods was investigated by oxygen uptake and thermal analysis on polymer samples containing various concentrations of components (100/0, 80/20, 40/60, 60/40, 20/80 and 100/0 w/w ). Drastic decrease in oxidation induction time was observed for low doses. The competition between crosslinking and scission has been examined on the basis of radical recombination on post-irradiation time. The influence of specimen formulations on oxidation induction time is discussed regarding to the contribution of antagonistic processes: crosslinking and oxidative degradation.     

Morphology and properties of PP/EPDM binary blends and PP/EPDM/nano‐CaCO3 ternary blends

In this article, the morphology, crystallization, and rheological behaviors of polypropylene (PP)/ethylene‐propylene‐diene terpolymer (EPDM) binary blend and PP/EPDM/calcium carbonate nanoparticles (nano‐CaCO₃) ternary blend were investigated. Two processing methods, i.e., direct extrusion and two‐step extrusion, were employed to prepare the PP/EPDM/CaCO₃ blend. The influence of EPDM and nano‐CaCO₃ respectively on phase morphology and properties of PP/EPDM blend and PP/EPDM/CaCO₃ blend were characterized by scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and dynamic rheometer. The crystallinity and crystallization temperature of PP/EPDM blend were improved in comparison to pure PP due to addition of EPDM, but kept invariable with the increased EPDM loading. As the EPDM content was increased, the mobility of PP molecular chains was weakened. Compared with direct extruded blend, less and finer nano‐CaCO₃ was dispersed in matrix of two‐step extruded blend. Accordingly, the increased nano‐CaCO₃ in matrix gave rise to a weaker increment in crystallinity and crystallization temperature of two‐step extruded blend, and a later platform of tanδ curve. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

汽车用三元乙丙橡胶改性聚丙烯

探讨了三元乙丙橡胶（EPDM）增韧聚丙烯的机理,讨论了影响三元乙丙橡胶/聚丙烯共混物韧性、刚性、流变性能、形态结构的因素及它们之间的相互关系,有助于设计和制造应用于汽车上的该种改性材料。     

PP／EPDM共混体系界面的研究

本文采用马来酸酐对三元乙丙橡胶（ＥＰＤＭ）进行熔融接枝改性,将性后的ＥＰＤＭ与聚丙烯（ＰＰ）共混,对ＰＰ／ＥＰＤＭ和ＰＰ／ＥＰＤＭ－ｇ－ＭＡＨ两种共混体系的界面状况进行了对比。运用Ｈｕｇｇｉｎｓ参数、界面张力参数对界面状况进行了表征;运用扫描电镜（ＳＥＭ）和偏光显微镜对共混物的冲击断口形貌以及结晶情况进行了观察与分析;探讨了界面状况与共混物力学性能以及流变性能间的关系。     

动态硫化PP/EPDM共混物的结构与性能

研究了动态硫化和直接共混对聚丙烯／三元乙丙橡胶共混物的力学性能、流动性能和形态结构的影响。结果表明：过氧化二异丙苯（DCP）的加入,使动态硫化和直接共混2种方法制备的共混物的熔体流动速率（MFR）增大,但直接共混的共混物的MFR较动态硫化共混物高。动态硫化共混物的粒径尺寸较直接共混物小,且分布均匀。动态硫化后的共混物中两组分的玻璃化转变温峰接近。DCP的加入使动态硫化共混物的缺口冲击强度明显高于直接共混的共混物。     

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.     

动态固化聚丙烯/马来酸酐接枝三元乙丙橡胶/环氧树脂共混物

将动态固化法成功地应用于聚丙烯／环氧树脂共混体系中，加入马来酸酐接枝三元乙丙橡胶后不仅增加了聚丙烯／环氧树脂共混体系的相容性，而且提高了聚丙烯基质的韧性。固化的环氧树脂颗粒提高了聚丙烯基质的刚性。动态固化聚丙烯／马来酸酐接枝三元乙丙橡胶／环氧树脂共混物的刚性和韧性达到了很好的平衡。     

反应性聚丙烯/三元乙丙橡胶共混物的流变性能研究

采用高压毛细管流变仪 ,研究了EPDM含量、交联剂、交联助剂等因素对反应性PP/EPDM共混物性能的影响。结果表明 ,EPDM分散相浓度为 2 0～ 2 5phr,反应共混工艺对体系的消缠降粘效果显著 ;交联剂A的含量越高 ,体系表观粘度越小 ,但粘度对剪切的响应不敏感 ;交联剂B和并用交联剂S可抑制PP降解 ,进一步优化材料力学性能 ,并仍保持体系加工流动性高于简单共混PP/EPDM。     

Compatibilization of PP/EPDM blends by grafting acrylic acid to polypropylene and epoxidizing the diene in EPDM

In this article, ethylene–propylene–diene‐rubber (EPDM) was epoxidized with an in situ formed performic acid to prepare epoxided EPDM (eEPDM). The eEPDM together with the introduction of PP‐g‐AA was used to compatibilize PP/EPDM blends in a Haake mixer. FTIR results showed that the EPDM had been epoxidized. The reaction between epoxy groups in the eEPDM and carboxylic acid groups in PP‐g‐AA had taken place, and PP‐g‐EPDM copolymers were formed in situ. Torque test results showed that the actual temperature and torque values for the compatibilized blends were higher than that of the uncompatibilized blends. Scanning electron microscopy (SEM) observation showed that the dispersed phase domain size of compatibilized blends and the uncompatibilized blends were 0.5 and 1.5 μm, respectively. The eEPDM together with the introduction of PP‐g‐AA could compatibilize PP/EPDM blends effectively. Notched Izod impact tests showed that the formation of PP‐g‐EPDM copolymer improved the impact strength and yielded a tougher PP blend. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3949–3954, 2006     

PP/POE及PP/EPDM共混改性研究

以茂金属聚烯烃弹性体(POE,乙烯-辛烯共聚物)和三元乙丙橡胶(EPDM)作为聚丙烯(PP)的增韧剂,研究了PP/POE及PP/EPDM共混物的加工性能及力学性能。研究结果表明,POE在加工性、增韧改性等方面比EPDM更具有优势。借助扫描电子显微镜(SEM)进一步探讨了共混物的形态结构与性能的关系。     

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.     

交联剂对动态硫化PP／EPDM中PP晶体及EPDM形态结构的影响

针对ＰＰ／ＥＰＤＭ动态硫化中有机过氧化物交联剂Ａ用量对试样拉伸,弯曲和冲击等性能所产生的较大的影响,采用偏光显微镜研究了不同交联剂Ａ用量下动态硫化ＰＰ／ＥＰＤＭ中连续相ＰＰ的晶体结构和分散相ＥＰＤＭ的形态结构特征。     

Effect of NR and EPDM on the rheology of HDPE/PP blends

Summary We studied melt-rheological properties of ternary blends of polypropylene and high-density polyethylene with an elastomer (natural rubber or ethylene-propylene-diene), at several blending ratios and shear rates. Measurements made on a cone-plate rheometer are presented and discussed as a function of blend composition. The effect of the shear rate on the viscosity and flow curve is discussed in terms of the exponent of the power low for a non-Newtonian liquid. The addition of an elastomer to the polyolefins blends changes the shape of the viscosity-composition curve; this change is discussed in terms of the possible morphology of the blend. Received: 25 September 1998/Revised version: 8 February 1999/Accepted: 9 February 1999     

Largely improved toughness of PP/EPDM blends by adding nano-SiO2 particles

As a part of long-term project aimed at super polyolefin blends, in this work, we report the toughness and phase morphology of polypropylene (PP)/EPDM/SiO₂ ternary composites. Two processing methods were employed to prepare PP/elastomer/filler ternary composites. One was called one-step processing method, in which the elastomer and the filler directly melt blended with PP matrix. Another one was called two-step processing method, in which the elastomer and the filler were mixed first, and then melt blended with pure PP. Two kinds of PP (grafted without or with maleic anhydride (PP-g-MA)) and SiO₂ (treated with or without coupling agent) were used to control the interfacial interaction among the components. The dependence of the phase morphology on interfacial interaction and processing method was investigated. It was found that the formation of filler-network structure could be a key for a simultaneous enhancement of toughness and modulus of PP and its formation seemed to be dependent on the work of adhesion (W_AB) and processing method. As the W_AB of PP/EPDM interface was much lower than that of PP/SiO₂ and EPDM/SiO₂, and the two-step processing method was used, the formation of filler-network structure was favorable. In this case, a super toughened PP ternary composite with the Izod impact strength 2-3 times higher than PP/EPDM binary blend and 15-20 times higher than pure PP could be achieved.     

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.     

Brittle-ductile transition in PP/EPDM blends: effect of notch radius

The toughness of polypropylene (PP)/ethylene-propylene-diene monomer (EPDM) blends was studied over wide ranges of EPDM content and temperature. In order to study the effect of notch radius (R), the toughness of the samples with different notch radii was determined from Izod impact test. The results showed that both toughness and brittle-ductile transition (BDT) of the blends were a function of R, respectively. At test temperatures, the toughness tended to decrease with increasing 1/R for various PP/EPDM blends. Moreover, the brittle-ductile transition temperature (T_BT) increased with increasing 1/R, whereas the critical interparticle distance (ID_c) reduced with increasing 1/R. Finally, it was found that the different curves of ID_c versus test temperature (T) for different notches reduced down to a master curve if plotting ID_c versus T_BT^m-T, where T_BT^m was the T_BT of PP itself for a given notch, indicating that T_BT^m-T was a more universal parameter that determined the BDT of polymers. This conclusion was well in agreement with the theoretical prediction.     

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。     

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.     

Effects of crosslinked elastomer particles on heterogeneous nucleation of isotactic PP in dynamically vulcanized EPDM/PP and EOC/PP blends

The isothermal and non-isothermal crystallizations of PP in neat form and in the TPVs EPDM/PP and EOC/PP were investigated using differential scanning calorimetry (DSC). The crystallization of PP was systematically studied by fitting mathematical models, and was later confirmed by X-ray diffraction (XRD) and by scanning electron microscopy (SEM). The experiments revealed that crosslinked elastomer particles first accelerated the primary nucleation of the PP matrix, acting effectively as a nucleating agent that reduces the induction time while increasing the nucleation efficiency. In the secondary nucleation regime (growth of spherulites), the crosslinked elastomer particles enhanced crystal growth rate, reducing the nucleation energy contribution from PP chain folding. Moreover, the crosslinked elastomer particles increased the final thickness of PP lamellae from that of neat PP, and this was corroborated by the XRD results. On comparing the two types of elastomer, it was found that the EOC particles were more effective in heterogeneous cell nucleation than the EPDM particles. The morphological study by SEM revealed completely altered PP spherulite size and shape, as well as their altered distribution, affected by heterogeneous nucleation effects of the crosslinked elastomer particles.