纳米SiO2对天然橡胶/聚丙烯共混型热塑性弹性体的改性

在双辊电热式塑炼机上采用动态硫化法制备了天然橡胶/聚丙烯共混型热塑性弹性体(NR/PP TPV)。考察了纳米S iO2的加入顺序及其用量对NR/PP TPV力学性能的影响,研究了纳米S iO2填充改性TPV的耐溶剂性能和耐热变形性能,并用扫描电镜(SEM)观察了其两相结构和断面形貌。结果表明,纳米S iO2先与NR混炼均匀,再加入小料和硫黄所得的NR母炼胶与PP制备的TPV力学性能较好,且最佳的纳米S iO2加入量为3份;纳米S iO2改性的NR/PP TPV具有良好的耐溶剂性能和耐热变形性能;纳米S iO2提高了NR与PP相间结合强度。     

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     

不同硫磺用量对MPU/TPEE动态硫化热塑性弹性体重复加工及热油老化前后物理机械性能的影响

采用高温开炼机制备了不同硫磺(S)用量的混炼型聚氨酯(MPU)/热塑性聚醚脂弹性体(TPEE)动态硫化热塑性弹性体(TPV),并探索了TPV重复加工性能和热油老化前后的物理力学性能。结果表明,随加工次数的增加,加入S后TPV的拉断强度先增加后减小,100%定伸强度逐渐下降;热油老化后,随S用量增加,TPV的拉断强度、100%定伸强度、断裂伸长率、硬度均呈现下降趋势,体积变化率减小,质量变化率不变。     

Properties of dynamically vulcanized ethylene–propylene–diene copolymer/polypropylene blends

In this study, vulcanized thermoplastic elastomers were produced through the formation of crosslinks with peroxide for different ratios of ethylene–propylene–diene copolymer to polypropylene. Mixing was performed with a twin‐screw extruder. Afterward, the yield, tensile strength, elastic modulus, elongation, Izod impact strength, hardness, melt flow index, Vicat softening point, heat deflection temperature, and density of the crosslinks were determined. The thermal transition temperatures and microstructure were determined with differential scanning calorimetry and scanning electron microscopy, respectively. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3895–3902, 2007     

纳米SiO2增强NR/LDPE热塑性弹性体的技术

采用动态硫化技术制备了纳米二氧化硅(SiO2)增强天然橡胶/低密度聚乙烯(NR/LDPE)共混型热塑性弹性体。研究了纳米SiO2对NR/LDPE弹性体力学性能、耐溶剂性能、耐热变形性能和热塑性能的影响,并对弹性体的断面形貌进行了SEM分析。结果表明:纳米SiO2通过细化交联NR分散相,使NR与LDPE两相的相容性改善,两相界面粘结强度提高;当纳米SiO2质量分数为0.03时,NR/LDPE弹性体的力学性能最好,并且具有较好的耐溶剂性、耐热变形性能和热塑性能。     

动态硫化三元乙丙橡胶/聚丙烯热塑性弹性体的研究进展

介绍动态硫化三元乙丙橡胶(EPDM)/聚丙烯(PP)热塑性弹性体(TPV)的发展历程、配合体系、动态硫化工艺、应用领域和发展前景。相较于传统橡胶,动态硫化TPV作为新一代橡胶产品的典型代表,无论在生产工艺还是性能上均具有较大优势,且TPV对环境的影响较小,符合绿色环保理念。未来EPDM/PP TPV的研究方向将主要集中在环保、低挥发性有机物、高性能化和多功能化等方面。     

Microstructure‐properties correlations in dynamically vulcanized nanocomposite thermoplastic elastomers based on PP/EPDM

Thermoplastic vulcanized (TPV) nanocomposites were prepared in a laboratory mixer using EPDM, polypropylene of different viscosities, maleic anhydride modified polypropylene, an organo‐clay, and a sulfur‐based curing system. Based on the obtained results from X‐ray diffraction, transmission electron microscopy (TEM), scanning electron microscopy (SEM), differential scanning calorimeter, and mechanical properties, the microstructure of the prepared nanocomposites was found to be sensitive to the viscosity difference between the two phases and the clay content. X‐ray diffraction and TEM images of the TPV nanocomposites showed that clay was nearly exfoliated and randomly distributed into the polypropylene phase. The SEM photomicrographs of the dynamically vulcanized thermoplastic elastomer samples showed that the rubber particles were dispersed through the polypropylene in form of aggregates and their size increased with the introduction of clay. The nanoscale dimensions of the dispersed clay resulted in a significant improvement of the tensile modulus of the TPV nanocomposite samples, from 20 to 90% depending on clay content and the viscosity ratio of PP/EPDM. In the PP nanocomposites, the clay layers act as nucleating agents, resulting in higher crystallization temperature and reduced degree of crystallinity. Moreover, the oxygen permeability in the TPV nanocomposites was found to be lower than in unfilled but otherwise similar materials. POLYM. ENG. SCI., 47:207–217, 2007. © 2007 Society of Plastics Engineers.     

Dynamic properties of rubber vibration isolators and antivibration performance of ethylene–propylene–diene monomer/nylon 6 blend systems

This article examines thermoplastic elastomers (TPEs) and thermoplastic vulcanizates (TPVs) as two types of elastomers from melt-blended and dynamically vulcanized ethylene–propylene–diene monomer (EPDM) rubber materials and nylon 6 plastic materials. A series of investigations were conducted on the mechanical properties, morphology, dynamic mechanical properties, hysteresis behavior, and dynamic antivibration properties with different nylon 6 contents. The experimental results showed that the incompatibility between EPDM and nylon 6 led to the easy destruction of the TPV materials in two interfacial polymers upon the application of an external force. Thus, after a dynamic vulcanization process, the mechanical properties of the EPDM/nylon 6 blends were not as good as those of the TPE materials. In terms of morphology, nylon 6 plastics were uniformly distributed in the EPDM/nylon 6 blends during the EPDM rubber phase before vulcanization was performed. After the dynamic vulcanization, phase inversion was produced in which rubber microparticles were formed and dispersed in the nylon 6 plastic phase. The results of dynamic mechanical analysis, compression vibration hysteresis behavior, and dynamic property antivibration experiments showed that the blends provided better vibration isolation and antivibration performance after the amount of nylon 6 was increased and EPDM and nylon 6 were blended through dynamic vulcanization. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

汽车密封系统用高(回)弹性Santoprene热塑性硫化胶(TPV)

热塑性弹性体(TPE)是一类具有橡胶和热塑性塑料综合优异性能材料,而热塑性硫化胶(TPV)就是TPE中制备出的一个分支.TPV可以通过动态硫化方式制备出来,它具有普通的硫化胶优异的密封性能,本文详细介绍了Santoprene牌TPV,多项物理性能及对比数据,可成为各种汽车密封系统多用途材料,还介绍了国内有相似产品的厂家...     

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。     

羧基丁腈橡胶/PA12热塑性弹性体的制备及性能研究

通过动态硫化法制备了羧基丁腈橡胶/聚酰胺12(XNBR/PA12)热塑性硫化橡胶(TPV),考察了XNBR羧基含量和XNBR/PA12橡塑比(质量比,下同)对TPV力学性能、流变性能、耐油性能和耐热空气老化性能的影响.结果表明,随着橡塑比的增大,TPV力学性能先上升后下降;当XNBR羧基含量为7％(质量分数,下同)、橡...     

三元乙丙橡胶/聚丙烯动态硫化热塑性弹性体的相态结构

用扫描电镜研究了三元乙丙橡胶(EPDM)聚/丙烯(PP)动态硫化热塑性弹性体(TPV)相态结构的形成过程,探讨了交联密度、制备工艺、螺杆转速对EPDM/PP TPV相态结构的影响。结果表明,采用以酚醛树脂为硫化剂的动态硫化工艺制备的EPDM/PP TPV,其相态结构实现了由EPDM和PP组成的双连续相到以EPDM为分散相、PP为连续相的转变;当硫化剂用量为7份时,橡胶相硫化速率和交联密度最大;当螺杆转速为180 r/m in时,反应性挤出工艺较之密炼机工艺制备的EPDM/PP TPV的橡胶粒子更细小、分散更均匀。     

Effect of the compatibility on the morphology and properties of acrylonitrile–butadiene rubber/polypropylene thermoplastic vulcanizates

In this study, the morphologies of three types of acrylonitrile–butadiene rubber (NBR)/polypropylene (PP) thermoplastic vulcanizates (TPVs) (with an NBR/PP blend ratio of 70/30) were compared. The TPVs were (1) an ultrafine fully vulcanized acrylonitrile–butadiene rubber (UFNBR)/PP TPV made by the mechanical blending of UFNBR with PP, (2) a dynamically vulcanized NBR/PP TPV without the compatibilization of maleic anhydride grafted polypropylene (MP) and amine‐terminated butadiene–acrylonitrile copolymer (ATBN), and (3) a dynamically vulcanized NBR/PP TPVs with the compatibilization of MP and ATBN. The influence of the compatibility therein on the size of the dispersed vulcanized NBR particles and the crystallization behavior of the PP in the TPVs and the resultant properties are also discussed. As indicated by Fourier transform infrared spectroscopy, scanning electron microscopy, differential scanning calorimetry, polarizing microscopy, dynamic mechanical thermal analysis, and rheological and mechanical testing, the compatibility was significantly improved by the reactive compatibilization of MP and ATBN, which led to a uniform and fine morphology. The compatibilization increased the crystallization rate and reduced the size of the spherulites of PP. On the other hand, it was found that the dispersed vulcanized NBR particles lowered the degree of crystallinity. The better the compatibility of the blend was, the lower the degree of crystallinity and the storage modulus were, but the higher the loss factor and the processing viscosity were. All TPVs showed almost the same oil resistance, but the TPV prepared with reactive compatibilization had the best mechanical properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

聚酰胺类TPV的研究进展

以聚酰胺为基体采用动态硫化工艺制备的热塑性动态硫化弹性体（TPV）是一类颇具发展潜力的热塑性弹性体（TPE）。目前很多高性能橡胶材料都可以采用聚酰胺类的TPV代替,特别是我国汽车工业的高速发展,为这种TPV的发展提供了巨大的空间。本文重点介绍了这类TPV的研究进展。     

Dramatic influence of compatibility on crystallization behavior and morphology of polypropylene in NBR/PP thermoplastic vulcanizates

In this study, the isothermal/nonisothermal crystallization behavior of polypropylene (PP) in acrylonitrile butadiene rubber (NBR)/PP thermoplastic vulcanizates (TPVs) prepared with three different processing methods, the compatibility effect therein, and the mechanism involved were studied. We concluded that the vulcanized NBR particles in TPVs act as heterogeneous nucleation centers and increase the number of nuclei. The crystallization rate of PP thereby increases and the growth of PP spherulites is restrained because of the isolation of vulcanized NBR particles. Since the addition of compatibilizer improves the compatibility of NBR and PP, the smaller and uniformly dispersed NBR particles are obtained, resulting in more and smaller PP crystals as well as higher crystallization rate, compared with Ultra-fine fully vulcanized NBR particles (UFNBR)/PP TPV and NBR/PP TPV without compatibilization. The isothermal crystallization kinetics of PP in TPVs obeys the Avrami equation, whereas the nonisothermal crystallization kinetics is well described by the equation of Mo et al.     

热塑性弹性体(TPE)简述(上)

叙述了热塑性弹性体(TPE)的结构特点、品种和性能,并对其中的主要品种TPS、TPO、TPV、TPU、TPEE、TPVC、TCPE以及TPA等进行了分别介绍。简述了TPE的不足与今后的发展方向。指出,TPE作为一种节能环保的橡胶新型原料,发展前景十分看好。     

热塑性弹性体(TPE)简述(下)

叙述了热塑性弹性体(TPE)的结构特点、品种和性能,并对其中的主要品种TPS、TPO、TPV、TPU、TPEE、TPVC、TCPE以及TPA等进行了分别介绍。简述了TPE的不足与今后的发展方向。指出,TPE作为一种节能环保的橡胶新型原料,发展前景十分看好。     

Influences of blend proportions and curing systems on dynamic,mechanical, and morphological properties of dynamically cured epoxidized natural rubber/high‐density polyethylene blends

Thermoplastic elastomers (TPEs) based on dynamically cured epoxidized natural rubber/high‐density polyethylene (ENR/HDPE) blends were prepared. Influence of the process oil, blend proportion, and curing systems were investigated. It was found that the oil‐extended thermoplastic vulcanizates (TPVs) exhibited better elastomeric properties and improved ease of the injection process. Increasing the proportion of ENR caused increasing elastic response of elongation at break, tension set properties, and tan δ. It was also found that the TPV treated with phenolic resin exhibited superior mechanical properties and the smallest vulcanized rubber domains. The TPV treated with the conventional peroxide co‐agent curing system showed superior strength properties but had poor elastomeric properties. POLYM. ENG. SCI., 2009. © 2008 Society of Plastics Engineers     

膨胀阻燃三元乙丙橡胶/聚丙烯热塑性硫化胶的性能

分析了膨胀型阻燃剂聚磷酸铵(APP)、季戊四醇(PER)的加入方式对三元乙丙橡胶(EPDM)/聚丙烯(PP)体系硫化特性的影响,研究了加入不同膨胀型阻燃剂及协效剂硼酸锌(ZB)、有机蒙脱土(OMMT)对动态硫化EPDM/PP热塑性硫化胶(EPDM/PPTPV)性能的影响。结果表明,在动态硫化前加入APP或PER时,EPDM/PP体系不能进行硫化;当APP的加入量为30份时,EPDM/PPTPV的综合力学性能较佳;在EPDM/PPTPV中同时加入APP、PER、三聚氰胺(MEL)时,随着三者加入量的增加,体系的阻燃性能增强,但拉伸强度明显降低,三者的最佳用量为30份APP、10份PER、10份MEL,此时体系的黏度与纯EPDM/PPTPV相当;加入ZB或OMMT时,EPDM/PPTPV的拉伸强度降低,且加入OMMT体系的阻燃效果优于加入ZB体系;加入OMMT时,在低剪切速率下,体系的黏度减小;在高剪切速率下,体系的黏度增大;加入ZB时,在低剪切速率下,体系的黏度与未加ZB体系相当;在高剪切速率下,体系的黏度增大。     

动态硫化EVA/BR热塑性弹性体的增强研究

采用动态硫化法制备了乙烯-醋酸乙烯共聚物(EVA)/顺丁橡胶(BR)共混型热塑性弹性体(TPE),通过在树脂相中添加HDPE的方式对复合体系进行增强,对其力学性能及断面微观结构进行了研究。结果表明,对于动态硫化EVA/BR共混型TPE,当HDPE填充量在0～30phr的范围内,其动态硫化产物均表现出TPE的特征;随着树脂相中HDPE用量的提高,复合体系的拉伸强度、撕裂强度、邵氏硬度趋于显著提高,断裂伸长率趋于缓慢增加,而扯断永久形变则始终低于25%;FE-SEM的观察表明,动态硫化TPE的拉伸断面上两相界面结合良好;刻蚀样品表面的硫化胶粒子的尺寸在5mm左右且均匀分散。