硫化体系对动态硫化EPDM/POE热塑性弹性体性能的影响

采用动态硫化的方法在Haake转矩流变仪上制备了三元乙丙橡胶/聚烯烃(EPDM/POE)热塑性弹性体(TPV),并分别对不同硫化体系和硫化剂用量对TPV交联密度和性能的影响进行了研究。结果表明,随硫化剂用量的增加,TPV的交联密度增大,其中硫黄硫化体系的TPV变化最明显;采用硫黄硫化体系和酚醛树脂硫化体系制备的TPV性能优于过氧化物硫化体系,并且DCP和硫黄分别在用量为0.5份,酚醛树脂在1.0份时性能较佳。     

New ways to improve the damping properties in high‐performance thermoplastic vulcanizates

The incorporation of viscoelastic materials represents an effective strategy to reduce the vibratory level of structural components. Thermoplastic vulcanizates (TPVs) are a special type of viscoelastic material that combines the elastomeric properties of rubbers with the easy processing of thermoplastics. In the present work, we propose innovative ways to improve the damping properties of high‐performance TPVs by using rubbers with carboxylic functionalities. For that, TPVs from physical blends of carboxylated hydrogenated acrylonitrile butadiene rubber (XHNBR) and polyamide 6 (PA6) were prepared. The chain dynamics of different mixed crosslink systems containing peroxide, metal oxides and hindered phenolic antioxidants were investigated in order to find the most suitable strategy to design a high‐performance TPV system with upgraded damping properties. The results indicate that the damping performance of the TPV system can be tailored by controlling the type and magnitude of the bonding interactions between the mixed crosslink system and the XHNBR rubber phase. Therefore, this study demonstrates the potential of TPV systems containing carboxylic rubbers as high‐performance damping materials. © 2020 Society of Chemical Industry     

交联剂用量对BR/EVA热塑性硫化胶性能的影响

采用动态硫化法制备了BR/EVA热塑性硫化胶(TPV),考查了硫化体系中硫黄用量对混炼胶的硫化行为、静态硫化胶的溶出物含量及性能的影响,并对BR/EVA型TPV的力学性能及微观结构进行了研究。结果表明,随着硫黄用量的提高,混炼胶硫化历程中的平坦期较长,但t90趋于明显降低,静态硫化胶溶出物含量及力学性能均呈下降趋势;当硫黄用量为0.5份时,静态硫化胶及BR/EVA TPV表现出良好的综合性能。显微镜照片表明,BR硫化胶的粒状物平均尺寸为5～10μm左右,较均匀地分散在EVA树脂基体中;FE-SEM的测试表明,TPV的断面平滑,TPV具有良好的形变回复性。     

Mechanical properties of thermoplastic elastomers based on silicone rubber and an ethylene–octene copolymer by dynamic vulcanization

Thermoplastic vulcanizates (TPVs) are a special class of thermoplastic elastomers that are generally produced by the simultaneous mixing and crosslinking of a rubber with a thermoplastic polymer at an elevated temperature. Novel peroxide‐cured TPVs based on blends of silicone rubber and the thermoplastic Engage (an ethylene–octene copolymer) have been developed. These TPVs exhibit very good overall mechanical and electrical properties. With an increasing concentration of dicumyl peroxide, the tensile strength, modulus, and hardness of the TPVs increase, whereas the elongation at break decreases. Significant correlations have been obtained from oscillating disc rheometer torque values with various physical properties, such as the modulus and tension set of the TPVs. The aging characteristics and recyclability of the silicone‐based TPVs are also excellent. Scanning electron microscopy photomicrographs of the TPVs have confirmed a dispersed phase morphology. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Multifunctional peroxide as alternative crosslink agents for dynamically vulcanized epoxidized natural rubber/polypropylene blends

Commonly used dicumyl peroxide (DCP) in combination with coagent, triallyl cyanurate (TAC), as a crosslinking agent is well acceptable for dynamically vulcanized rubber phase of thermoplastic vulcanizates (TPVs). However, it generally produces volatile decomposition products, which cause a typical unpleasant smell and a blooming phenomenon. In this work, influence of two types of multifunctional peroxides: 2,4‐diallyloxy‐6‐tert‐butylperoxy‐1,3,5‐triazine (DTBT) and 1‐(2‐tert‐butylperoxyisopropyl)‐3‐isopropenyl benzene (TBIB), on properties of TPVs based on epoxidized natural rubber (ENR)/polypropylene (PP) blends were investigated. The conventional peroxide/coagent combinations, i.e., DCP/TAC and tert‐butyl cumyl peroxide (TBCP)/α‐methyl styrene (α‐MeS) were also used to prepare the TPVs for a comparison purpose. The TPVs with multifunctional peroxide, DTBT, provided good mechanical properties and phase morphology of small dispersed vulcanized rubber domains in the PP matrix which were comparable with the DCP/TAC cured TPVs. However, the TPVs with TBIB/α‐MeS and TBCP/α‐MeS showed comparatively low values of the tensile properties as well as rather large phase morphology. The results were interpreted by three main factors: the kinetic aspects of the various peroxides, solubility parameters of respective peroxide/coagent combinations in the ENR and PP phases, and the tendency to form unpleasantly smelling byproducts. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Systematic investigation on the effect of crosslinking agent type and dosage on the performance of TPU/MVQ based thermoplastic vulcanizates

Dynamic vulcanized thermoplastic polyurethane (TPU)/methyl vinyl silicone rubber (MVQ) thermoplastic vulcanizates (TPVs) were prepared in torque rheometer. The influence of the type and amount of peroxide crosslinking agent on the mechanical properties, thermal stability, micromorphology and melt flowability was systematically investigated. The results showed that the mechanical properties of the TPVs vulcanized by 2,5-dimethyl-2,5-di (tert-butyl peroxy) hexane (DBPH) first increased and then decreased with increasing the peroxide amount, while for dicumyl peroxide (DCP) vulcanizing system the mechanical properties slowly increased. Besides, the comprehensive mechanical properties vulcanized by DBPH were better than those of DCP group. The results of the thermogravimetric analysis showed that the TPVs vulcanized by DBPH had better heat stability, corresponding to the excellent thermo-oxidative aging performance and the 38% increase in tensile strength after aging. In addition, the MVQ rubber particles showed better dispersing performance for DBPH vulcanizing system. The melt flow rate of the TPVs showed a linear relationship with increasing DBPH dosage and became worse after the amount of crosslinking agent exceeded 1.5 phr. By comprehensive comparison, the TPVs have better performance when use peroxide DBPH as the crosslinking agent and the dosage is 1.5 phr.     

Influence of DCP content on the toughness and morphology of fully biobased ternary PLA/NR-PMMA/NR TPVs with co-continuous phase structure

ABSTRACT

Herein, the poly(lactic acid) (PLA)/poly(methyl methacrylate)-grafted natural rubber (NR-PMMA)/natural rubber (NR) blends with improved compatilibility was prepared by dicumyl peroxide induced dynamic vulcanization. Both the simple blend and the PLA/NR-PMMA/NR ternary thermoplastic vulcanizates (TPVs) exhibited co-continuous morphology. Moreover, the in situ compatibilization between PLA and rubber took place during the dynamic vulcanization. With increasing the DCP content, the toughness first increased and then decreased. With 2.5 phr DCP, the TPV displayed the highest impact strength of 760.7 J/m. Meanwhile, tensile strength of the TPVs was almost unchanged to that of the simple blend with the values of ~ 44 MPa.     

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。     

HNBR/EPDM blends: Covulcanization and compatibility

The covulcanization characteristics, mechanical properties, compatibility, and hot‐air aging resistance of hydrogenated nitrile‐butadiene rubber (HNBR)/ethylene‐propylene‐diene rubber (EPDM) blends cured with either sulfur or dicumyl peroxide (DCP) were studied. The difference between M_H and M_L (M_H ? M_L), rheometer graphs, selective swelling and a dynamic mechanical analysis of HNBR/EPDM blends confirmed that the peroxide curing system gives better covulcanization characteristics than the sulfur curing system and peroxide exhibited higher crosslink efficiency on EPDM while sulfur showed larger crosslink efficiency on HNBR. Dynamic mechanical analysis and morphology indicated that the compatibility between HNBR and EPDM is limited. Tensile strength and elongation at break of the sulfur‐cured blends are greater than those obtained with peroxide and increase with the HNBR fraction. The blends crosslinked with peroxide retain their tensile strength but not their elongation at break after hot air ageing better than blends vulcanized by sulfur. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Dynamically vulcanized blends of polypropylene and ethylene octene copolymer: Influence of various coagents on mechanical and morphological characteristics

Dynamically cured blends of polypropylene (PP) and ethylene octene copolymer (EOC) with coagent‐assisted peroxide curative system were prepared by melt‐mixing method. It was well established that PP exhibits β‐chain scission in the presence of peroxide. Principally, incorporation of a coagent increases the crosslinking efficiency in the EOC phase and decreases the extent of degradation in the PP phase. The present study mainly focused on the influence of three structurally different coagents, namely, triallyl cyanurate (TAC), trimethylol propane triacrylate (TMPTA), and N,N′‐m‐phenylene dimaleimide (MPDM), on the mechanical properties of the PP/EOC thermoplastic vulcanizates (TPVs). The reactivity and efficiency of different coagents were characterized by cure study on EOC gum vulcanizate. TAC showed the highest torque values followed by MPDM and TMPTA. Significant improvements in the physical properties of the TPVs were inferred with the addition of coagents. Among the three coagents used, MPDM showed the best balance of mechanical properties in these TPVs. The results indicated that torque values obtained during mixing and the final mechanical properties can be correlated. Different aspects were explained for the selection of a coagent that forms a product with desired properties. The phase morphologies of the TPVs prepared were studied by scanning electron microscopy. Tensile fracture patterns were also analyzed to study the failure mechanism of the samples. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

NR/PP thermoplastic vulcanizates: Selection of optimal peroxide type and concentration in relation to mixing conditions

Thermoplastic vulcanizates (TPVs) from natural rubber (NR) and polypropylene (PP) were studied, prepared by dynamic vulcanization during melt mixing, using various peroxides to crosslink the rubber phase. The objective was to find a proper balance between degree of crosslinking of the rubber and degradation of the PP‐phase, and the tendency of the peroxide to form smelly by‐products, in particular acetophenone. Four types of peroxides were investigated: 2,5‐dimethyl‐2,5‐di(tert‐butyl‐peroxy) hexyne‐3 (DTBPHY), 2,5‐dimethyl‐2,5‐di(tert‐butyl‐peroxy) hexane (DTBPH), di(tert‐butylperoxyisopropyl) benzene (DTBPIB), and dicumyl peroxide (DCP), at two mixing temperatures: 160 and 180°C for a 60/40 NR/PP TPV. The maximum and final mixing torques are clearly related to the intrinsic decomposition temperature of the particular peroxide used, where DCP and DTBPIB turn out to be effective at 160°C, whereas the other two require a higher temperature of 180°C. The best mechanical properties, tensile strength, elongation at break and compression set are obtained at lower mixing temperature with DCP and DTBPIB, presumably due to less degradation of the NR and PP. Unfortunately, these two peroxides form more smelly by‐products than DTBPHY and DTBPH. Dependent on the requirements of the pertinent application, a balanced selection needs to be made between the various factors involved to obtain an optimal product performance of these NR/PP TPVs. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Design and properties of a series of high‐temperature thermoplastic elastomeric blends from polyamides and functionalized rubbers

A series of high‐temperature thermoplastic elastomers (TPEs) and thermoplastic vulcanisates (TPVs) were successfully developed based on two different types of heat resistant polyamide (PA) (25 parts by weight)—PA‐12 and PA‐6, in combination with three different functionalized rubbers (75 parts by weight) of varying polarity, e.g., maleic anhydride grafted ethylene propylene diene terpolymer (MA‐g‐EPDM), sulphonated ethylene propylene diene terpolymer, and carboxylated acrylonitrile butadiene rubber, by melt mixing method. These rubbers have low level of unsaturation in its backbone, and the plastics showed high melting range. Thus, the developed TPEs and TPVs were expected to be high temperature resistant. Resol type resin was used for dynamic vulcanization to further increase the high temperature properties of these blends. Interestingly, initial degradation temperature of the prepared blends was much higher (421 °C for MA‐g‐EPDM/PA‐12) than the other reported conventional TPEs and TPVs. Fourier transform infrared analysis described the interactive nature of the TPEs and TPVs, which is responsible for their superior properties. The maximum tensile strength with lowest tension set was observed for the carboxylated acrylonitrile butadiene rubber/PA‐12 TPV. Mild increase in mechanical properties without any degradation was observed after recycling. Dynamic mechanical analysis results showed two distinct glass transition temperatures and indicated the biphasic morphology of the blends, as evident from the scanning electron microscopy. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45353.     

Effect of dicumyl peroxide and phenolic resin as a mixed curing system on the mechanical properties and morphology of TPVs based on HDPE/ground tire rubber

Thermoplastic vulcanizates (TPVs) are a special group of thermoplastic elastomer with the characteristic that consists of rubber elasticity and the processability of thermoplastic polymers. TPVs based on high density polyethylene (HDPE)/ground tire rubber (GTR) with phenolic resin (HY‐2045) and dicumyl peroxide (DCP) as vulcanizing agents are prepared through dynamic vulcanization in this article. The blends consisting of 40/60 HDPE/GTR are melt‐mixed in an internal mixer and then pressed with a compression molding machine. The aim of this experiment is to study the influence of a compound curing agent system on the mechanical properties of the HDPE/GTR composites. The results indicate that the mechanical properties of the HDPE/GTR blends are improved significantly by adding 4 phr HY‐2045 and 0.3 phr DCP than those of TPVs without any vulcanizing agents after dynamic vulcanization. The X‐ray photoelectron spectroscopy study and the FTIR‐ATR analysis confirmed that the crosslinking phenomenon occurred in the preparation of TPVs; and the gel fraction analysis indicates that the GTR components and the HDPE components of the HDPE/GTR blends are all moderately crosslinked. In addition, the morphology of the HDPE/GTR blends has been investigated by scanning electron microscopy. POLYM. COMPOS., 36:1907–1916, 2015. © 2014 Society of Plastics Engineers     

Development of novel polar thermoplastic vulcanizates based on ethylene acrylic elastomer and polyamide 12 with special reference to heat and oil aging

Thermoplastic vulcanizates (TPVs) based on ethylene acrylic elastomer (AEM) and polyamide 12 (PA12) have been developed by the dynamic vulcanization process, in which selective cross‐linking of the elastomer phase (AEM) during melt mixing with the thermoplastic phase (PA12) has been carried out simultaneously. TPVs at varied blend ratios (50 : 50, 60 : 40, 70 : 30) of AEM/PA12 were prepared at 185°C at a rotor speed of 80 rpm up to 5 min of mixing. Di‐(2‐tert‐butyl peroxy isopropyl) benzene (DTBPIB) was chosen as the suitable cross‐linking peroxide to carry out the dynamic vulcanization. Morphology study reveals the development of continuous agglomerate of rubber network in case of all the TPVs took place and the average dimension of the rubber particles are in the range of 30–40 nm. TPV based on 50 : 50 AEM/PA12 shows better physicomechanical properties, thermal stability, and dynamic mechanical behavior among all the TPVs. For aging test, TPVs were exposed to air, ASTM oil 2 and 3. Air aging tests were carried out in hot air oven for 72 h at 125°C, while the oil aging tests were carried out after immersion of the samples into the oils in an aging oven. After aging, there are only slight deterioration of physicomechanical properties of the TPVs. Particularly in case of 50 : 50 blend of AEM/PA12, the retention of the properties even after aging was found excellent. The recyclability of these new TPVs is also found to be excellent leading to find potential application in automotives. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42655.     

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     

动态硫化丁腈橡胶/尼龙6热塑性弹性体的制备及性能

采用动态硫化法制备了丁腈橡胶/尼龙6热塑性弹性体(NBR/PA 6 TPV),考察了硫化体系、羧基丁腈橡胶(XNBR)以及增塑剂高密度氧化聚乙烯蜡(AC-316 A)和正丁基苯磺酰胺(BBSA)对TPV硫化特性、力学性能和微观形貌的影响。结果表明,以促进剂HVA-2/促进剂DM为硫化体系,动态硫化过程体系黏度的变化比以酚醛树脂/SnCl2为硫化体系时更平稳;但用后者制备TPV,其撕裂强度和扯断伸长率等力学性能更优,PA 6的结晶度更低。XNBR能对NBR和PA 6起到增容作用,当XNBR与NBR的质量比为10/90时,TPV的力学性能最好,NBR在PA 6中分散得最均匀。AC-316 A和BBSA都能对TPV起到增塑作用,随其用量的增加,体系黏度降低。     

Dynamically vulcanized blends of polypropylene and ethylene octene copolymer: Influence of various coagents on thermal and rheological characteristics

The present study focuses on the influence of the three structurally different coagents, namely triallyl cyanurate (TAC), trimethylol propane triacrylate (TMPTA) and N,N′‐m‐phenylene dimaleimide (MPDM) on the thermal and rheological properties of thermoplastic vulcanizates (TPVs) based on the polypropylene (PP) and ethylene octene copolymer (EOC). Depending on the structure and reactivity, different coagents show different behaviors. All the TPV compositions were made by melt mixing method in a Haake Rheomix at 180°C. Rheological properties have also been evaluated at the same temperature. Viscoelastic properties of the TPVs were analyzed by a dynamic oscillatory rheometer in the melt state in a Rubber Process Analyzer (RPA 2000). Morphologically, TPVs consist of dense crosslinked rubber domains dispersed in a continuous thermoplastic matrix. The crosslinked rubber particles have a tendency to form agglomerates and build local clusters which undergo disintegration by shearing. A variety of rheological characteristics such as Payne effect, shear rate sensitivity, modulus recovery and dynamics of relaxation were studied by performing strain sweep, frequency sweep and stress relaxation tests. Among the various coagents taken for investigation, MPDM‐based TPVs show improved dynamic functions (complex modulus and complex viscosity) and lower rate of stress relaxation over TAC, TMPTA and the control sample without any coagent. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Cure characteristics and mechanical properties of short nylon fiber‐reinforced nitrile rubber composites

Acrylonitrile butadiene rubber (NBR)‐based composites were prepared by incorporating short nylon fibers of different lengths and concentration into the matrix using a two‐roll mixing mill according to a base formulation. The curing characteristics of the samples were studied. The influence of fiber length, loading, and rubber crosslinking systems on the properties of the composites was analyzed. Surface morphology of the composites has been studied using Scanning Electron Microscopy (SEM). Addition of nylon fiber to NBR offers good reinforcement, and causes improvement in mechanical properties. A fiber length of 6 mm was found to be optimum for the best balance of properties. It has been found that at higher fiber loadings, composites show brittle‐type behavior. Composites vulcanized by the dicumyl peroxide (DCP) system were found to have better mechanical properties than that by the sulfur system. The swelling behavior of the composites in N,N‐dimethyl formamide has been analyzed for the swelling coefficient values. Composites vulcanized in the DCP system were found to have higher rubber volume fraction than that in the sulfur system, which indicates better rubber–fiber interaction in the former. The crosslink densities of various composites were also compared. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1023–1030, 2004     

Influence of accelerator/sulphur and co-agent/peroxide ratios in mixed vulcanisation systems on cure characteristics,mechanical properties and heat aging resistance of vulcanised SBR

The influence of accelerator/sulphur and co-agent/peroxide ratios on cure characteristic and vulcanisate properties in mixed vulcanisation of styrene butadiene rubber (SBR) was investigated in this work. Accelerator/sulphur ratio was investigated with three alternative sulphur curing systems, namely conventional, semi-efficient and efficient vulcanisation (EV) systems. Zinc dimethacrylate (ZDMA) was used as a co-agent to enhance the performance of peroxide and to provide ionic linkages. Ionic linkages contributed by ZDMA create bridges between two polymer chains. The ZDMA/peroxide ratio was varied from 2 to 10. The concentration of dicumyl peroxide was held fixed while the ZDMA content was varied. Cure characteristics, mechanical properties, dynamic mechanical properties and heat aging resistance were investigated in relation to the crosslink structure. Increasing the ZDMA/peroxide ratio significantly increased density of ionic linkages, especially in combination with the EV system. The combination of EV system with high ZDMA/peroxide ratio provided the highest ionic crosslink density and the lowest polysulphidic crosslink density: this enhanced the mechanical properties, the dynamic mechanical properties and the thermal stability of SBR vulcanisates.     

Study on the microstructure and properties of bromobutyl rubber (BIIR)/polyamide‐12 (PA12) thermoplastic vulcanizates (TPVs)

In this study, polyamide‐12 (PA12)/brominated isobutylene‐isoprene (BIIR) TPVs with good mechanical properties and low gas permeability were prepared by dynamic vulcanization in a twin‐screw extruder. The effects of three kinds of compatibilizers on the microstructure and properties of BIIR/PA12 TPV were studied. The compatibility between BIIR and PA12 was improved when maleated hydrocarbon polymeric compatibilizer is added. The reaction between maleic anhydride and amine in polyamide leads to the in situ formation of hydrocarbon polymer grafted polyamide which subsequently can be used to lower the interfacial tension between BIIR and polyamide. The compatibilizing effect of maleic anhydride modified polypropylene (PP‐g‐MAH) on BIIR/PA12 blends is the best among these compatibilizers because the surface energy of PP‐g‐MAH is very close to that of BIIR. The dispersed rubber phase of the blend compatibilized by PP‐g‐MAH shows the smallest size and more uniform size distribution, and the resulting TPVs show the best mechanical properties. The effects of fillers on the properties of BIIR/PA12 TPV were also investigated. The size of the BIIR phase increases with the increase in the content of CaCO₃. The modulus and tensile strength of TPVs increased with the increase in the content of CaCO₃ because of the reinforcing effect of CaCO₃ on TPVs. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43043.