Oil-resistance studies of dynamically vulcanized poly(vinyl chloride)/epoxidized natural rubber thermoplastic elastomer

Dynamically vulcanized poly(vinyl chloride)/epoxidized natural rubber (PVC/ENR) thermoplastic elastomers (TPEs) were prepared with a Brabender plasticorder coupled with a mixing attachment by melt mixing. The blends were prepared at 150°C at a rotor speed of 50 rpm. Curatives concentration was steadily increased from 0 to 1 phr in order to study the vulcanization effect on the plasticized blend. The effectiveness of the dynamic vulcanization was indicated by the Brabender plastograms. The properties investigated include mass swell, tensile strength, elongation at break, modulus at 100% elongation (M100), tear strength, and hardness. The PVC/ENR samples were exposed to two types of environments, namely, air and oil under otherwise identical conditions. The effect of oil and thermooxidative aging on the mechanical properties were characterized at room temperature and 100°C. It was found that at ambient temperature the samples immersed in oil possessed similar properties to those that were exposed to air. Significant enhancement in mechanical properties were observed for both environments at 100°C. This has been attributed to the increase in crosslink density which was manifested by a steady reduction in percent mass swell with increased sulfur loading. The excellent mechanical behavior of the PVC/ENR TPEs even after immersing the samples in oil at 100°C has provided a good indication of the oil resistance of the materials. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1357–1366, 1998     

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.     

过氧化物硫化体系对CM／XNBR共混物性能的影响研究

研究了不同用量过氧化物硫化体系对氯化聚乙烯橡胶（CM）／羧基丁腈橡胶（XNBR）共混硫化胶各相交联密度及热空气老化前后的物理机械性能、耐油性能等的影响规律。结果表明,随硫化体系用量的增加,共混硫化胶两相的交联密度都明显增加,交联密度差值变大;焦烧时间逐渐降低;硬度、拉伸强度、100％定伸应力、体积磨耗量呈上升趋势,永久变形、扯断伸长率明显降低,撕裂强度整体变化不大,常温下体积和质量变化率均很小,高温下体积和质量变化率明显降低后趋于平稳;热空气老化后,硬度、拉伸强度、100％定伸应力、撕裂强度整体上升,扯断伸长率整体下降,体积磨耗量整体变化不大;热油老化后,拉伸强度、100％定伸应力变化不大,扯断伸长率明显降低。     

The Effect of Dynamic Vulcanization on the Properties of Polypropylene/Ethylene-Propylene Diene Terpolymer/Natural Rubber (PP/EPDM/NR) Ternary Blend

The effects of dynamic vulcanization on the process development and some properties, such as tensile properties, swelling index, gel content, crystallinity, and morphology, of the polypropylene (PP)/ethylene-propylene diene terpolymer (EPDM)/natural rubber (NR) blends were investigated. Dynamically vulcanized blends show higher stabilization torque than unvulcanized blends. In terms of tensile properties, the tensile strength and tensile modulus (stress at 100% elongation, M₁₀₀) of the vulcanized blends have been found to increase as compared with the unvulcanized blends, whereas the elongation at break is higher in the blend with richer EPDM content. These results can be attributed to the formation of cross-linking in the rubber phase. The formation of cross-links in the rubber phase has also been proved by swelling index and gel content. The percentage of crystallinity of the blends is decreased by dynamic vulcanization. Scanning electron microscopy (SEM) micrographs from the surface extraction of the blends support that the cross-links occurred during dynamic vulcanization.     

Vulcanization characteristics and mechanical properties of natural rubber–scrap rubber compositions filled with leather particles

Scrap rubber recycling combined with waste leather particles in natural rubber compounds has been studied. The effect of leather and scrap rubber loading on vulcanization characteristics of natural rubber compounds has been evaluated. The presence of leather was found to reduce the scorch time and increase the maximum and minimum torque. While reversion was not observed in the absence of leather at 150 °C, it was more prominent when leather was incorporated. Mechanical properties such as tensile strength, elongation at break, tear strength, modulus and hardness were found to increase on increasing the scrap rubber loading in the absence of leather. Compounds containing leather exhibited higher tensile strength, modulus, hardness and tear strength values but the modulus and hardness values were found to decrease as the scrap rubber loading increased. All the vulcanizates exhibited only limited swelling in different media as the swelling of one phase of the composite was found to be restricted by the other phase. Copyright © 2004 Society of Chemical Industry     

超临界二氧化碳发泡EPDM/LDPE热塑性弹性体微孔泡沫

本文通过熔融共混制得了EPDM/LDPE热塑性弹性体,压制标准试样,然后使用超临界二氧化碳作为发泡剂在高压反应釜中进行物理发泡。通过万能拉力机测试了弹性体力学性能,用扫描电镜观察了拉伸断面和泡孔的微观结构。结果表明：DCP硫化体系的热塑性弹性体的综合力学性能要优于硫黄硫化体系,随着硫化剂用量的增多,拉伸强度和撕裂强度有一个最大值,硬度上升;橡塑比在4:6时,力学性能达到最佳,最大拉伸强度为7.5MPa,最大撕裂强度为27.6MPa。扫描电镜观察其拉伸断面形貌,表明EPDM橡胶相与LDPE塑料相呈现“海-岛”两相微观结构;泡孔大小均匀性较好,成功制备了微米级微孔泡沫且泡孔大小分布均匀。     

NR/SBR并用胶配比对其硫化特性和力学性能的影响

考察了天然橡胶与丁苯橡胶不同配比对并用胶硫化特性和力学性能的影响.无转子硫化仪的测试结果表明,随着丁苯橡胶的占比增加,最小转矩和最大转矩均变大,且两者差值也随之增大,硫化时间延长,硫化胶的拉伸强度和撕裂强度明显下降,硬度增加;120℃老化后拉伸强度有不同程度的下降,天然橡胶占比越多下降越明显.     

Solvent resistance and mechanical properties in thermoplastic elastomer blends prepared by dynamic vulcanization

Dynamic vulcanization was used to prepare thermoplastic elastomer blends of nylon (polyamide), polypropylene (PP) and polybutylene terephthalate thermoplastics with chlorobutyl (CIIR) and nitrile (NBR) rubbers. Mechanical properties of the blends were correlated against composition. Although hardness and tensile strength increase with increasing thermoplastic content for all blends, elongation at break values initially decrease and then increase in the range of 20–40% thermoplastic. For various blend compositions, the swelling behavior was evaluated with solvents that are able to dissolve the uncured rubber portion but not the thermoplastic component of the mixtures. All five systems showed swelling index values that were substantially less than the calculated “theoretical” values of swelling index. This was attributed to a caging effect of the thermoplastic component on the rubber phase, which restricts access of solvent and swelling of the rubber phase. In turn, this affects the solvent resistance of the blend. Some of the blends were evaluated by differential scanning calorimetry to assess the compatibility of the components in the blend. scanning electron microscopy was also used to determine the degree of compatibility of the two phases generated in the mixing process. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of oil contents in dynamically cured natural rubber and polypropylene blends

Mechanical, dynamic, thermal, and morphological properties of dynamically cured 60/40 NR/PP TPVs with various loading levels of paraffinic oil were investigated. It was found that stiffness, hardness, tensile strength, storage shear modulus, complex viscosity, glass transition temperature (T_g) of the vulcanized rubber phase, degree of crystallinity and crystalline melting temperature (T_m) of the polypropylene (PP) phase decreased with increasing loading levels of oil. This is attributed to distribution of oil into the PP and vulcanized rubber domains causing oil‐swollen amorphous phase and vulcanized rubber domains. An increasing trend of elastic response in terms of tension set and damping factor was observed in the TPVs with loading levels of oil in a range of 0–20 phr. It is supposed that a major proportion of oil was first preferably migrated into the PP phase and caused an abrupt decreasing trend of degree of crystallinity and T_m of the PP phase. The dispersed vulcanized rubber domains remained small as particles with a low degree of swelling. Increasing loading levels of oil higher than 20 phr caused a decreasing trend of elongation at break and elastomeric properties. Saturation of oil in the PP phase was expected and the excess oil was transferred to the rubber phase which thereafter caused larger swollen vulcanized rubber domains. The remaining amount of oil was able to separate as submicron pools distributed in the PP matrix. This caused lowering of T_g, T_m, crystallinity of PP phase as well as strength, elastomeric, and dynamic properties of the TPVs. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

Properties of Polypropylene (PP)/Ethylene-Propylene Diene Terpolymer (EPDM)/Natural Rubber (NR) Vulcanized Blends: The Effect of N,N-m-Phenylenebismaleimide (HVA-2) Addition

This paper discusses process development, tensile properties, morphology, oil resistance, gel content, and thermal properties of polypropylene (PP)/ethylene-propylene diene terpolymer (EPDM)/natural rubber (NR) vulcanized blends with the addition of N,N-m-phenylenebismaleimide (HVA-2) as a compatibilizer. Blends were prepared in several blend ratios in a Haake Polydrive with temperature and rotor speed of 180°C and 50 rpm, respectively. Results indicated that the combination of dicumyl peroxide (Dicup) with HVA-2 shows high torque development and stabilization torque as compared to the blend with Dicup vulcanization alone. In terms of tensile properties, the combination of Dicup with HVA-2 shows higher tensile strength, tensile modulus (M₁₀₀), elongation at break, oil resistance, and gel content in all blend ratios compared to similar vulcanized blends with Dicup without HVA-2 addition. Scanning electron microscope (SEM) micrographs of the blends support that the cross-linking and compatibilization occur during the process of the vulcanized blend containing HVA-2. In the case of crystallinity of the blends, the addition of HVA-2 in Dicup vulcanized blend revealed a tendency for the percentage of crystallinity (Xc) to decrease. The addition of HVA-2 in Dicup vulcanization also produced blends with good thermal stability dealing with the so-called coagent bridge formation.     

天然橡胶与甲基硅油的相容性研究

研究了不同硫化体系和不同硫化剂用量的天然橡胶与甲基硅油的相容性。结果表明,硫黄硫化胶与甲基硅油具有较好相容性,其中半有效硫化体系硫化胶在85℃硅油中浸泡168h后力学性能最好,拉伸强度仍高达17.8MPa,质量变化率只有1.41%,基本不溶胀。     

Ethylene vinyl acetate as compatibilizer on cure characteristics and mechanical properties of (natural rubber)/(Recycled acrylonitrile‐butadiene rubber) blends

Ethylene vinyl acetate (EVA) has been used as a compatibilizer for (natural rubber)/(recycled acrylonitrile‐butadiene rubber) (NR/NBRr) blends, vulcanized by sulfur. EVA offers excellent heat, ozone, and weather resistance, whereas the vinyl acetate groups provide oil resistance to the blend. It exhibits good tear resistance and may be crosslinked. However, EVA exhibits poor low‐temperature flexibility. NBR gloves have excellent resistance to punctures, tears, and many types of chemicals, while NR has good physical and mechanical properties. NR/NBRr blends were prepared with various compositions with the EVA content fixed. Tensile properties, hardness, and swelling behavior tests were performed to determine the compatibility of NR/NBRr blends in the presence of EVA. Results indicated that incorporation of EVA into NR/NBRr blends improved tensile strength, modulus, and elongation at break compared with NR/NBRr blends without EVA. The improvement in hardness and reduction in resilience on compatibilization are due to an increase in crosslink density, which gives NR/NBRr blends better swelling resistance. Scanning electron microscopy of the fracture surfaces indicates that, with the addition of EVA in NR/NBRr blends, better adhesion between NR and NBRr was obtained, thus improving the compatibility of NR/NBRr blends. J. VINYL ADDIT. TECHNOL., 23:135–141, 2017. © 2015 Society of Plastics Engineers     

丁腈橡胶/乙丙橡胶并用胶性能的研究

研究丁腈橡胶(NBR)/三元乙丙橡胶(EPDM)并用比对力学性能、老化性能和耐油性能的影响以及增容剂对共混胶性能的影响.结果表明,在NBR/EPDM共混胶中随EPDM用量的增加,硫化胶的硬度、拉伸强度、撕裂强度和定伸应力呈现下降趋势、拉断伸长率及耐低温性能有所改善,降低了NBR的耐汽油性能,但提高了耐含乙醇汽油性能.随着增容剂CM用量的增加,硫化胶拉伸强度、撕裂强度、100％定伸应力及硬度都呈增大趋势,采用扫描电镜可以清晰的看到添加CM改性后NBR/EPDM共混胶相容性得到显著改善.     

Thermoplastic vulcanizates based on epoxidized natural rubber/polypropylene blends: Effect of epoxide levels in ENR molecules

Epoxidized natural rubbers (ENR) with various levels of epoxide groups were prepared. Thermoplastic vulcanizates based on 75/25 ENRs/PP blends with Ph‐PP compatibilizer were later prepared by dynamic vulcanization using sulfur curing system. Influence of various levels of epoxide groups on rheological, mechanical morphological properties, and swelling resistance of the TPVs was investigated. It was found that the mixing torque, apparent shear stress, apparent shear viscosity, tensile strength, and hardness properties increased with increasing levels of epoxide groups in the ENR molecules. This may be attributed to increasing level of chemical interaction between the methylol groups of the Ph‐PP molecules and polar functional groups of the ENR molecules. Also, the PP segments in the Ph‐PP molecules are capable of compatibilizing with the PP molecules used as a blend composition. In SEM micrographs, we observed finer dispersion of vulcanized rubber domains as increasing levels of epoxide contents. This corresponds to increasing trend of strength and hardness properties of the TPVs. An increasing trend of tension set and a decreasing trend of elongation at break were observed as increasing levels of epoxide groups in the ENR molecules. This is because of higher rigidity of the vulcanized ENR phase with higher epoxide groups. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3046–3052, 2006     

The effect of an epoxidized plasticizer on the thermo-oxidative ageing of poly(vinyl chloride)/epoxidized natural rubber thermoplastic elastomers

The effects of an epoxidized plasticizer on the mechanical properties and thermo-oxidative ageing behaviour of poly(vinyl chloride)/epoxidized natural rubber thermoplastic elastomers (TPEs) were investigated. Aged and unaged blends were characterized by FTIR, tensile properties, tear strength, hardness and dynamic mechanical analysis (DMA). The properties of the epoxidized soya oil (ESO) plasticized TPEs were compared with those of the di-2-ethylhexylphthalate (DOP) plasticized counterparts. The presence of epoxide groups in ESO has been shown to produce two conflicting effects. On the one hand, the presence of excessive epoxide groups has resulted in poor ageing behaviour. On the other hand, it has resulted in a good interaction and compatibility with PVC/ENR. It was found that the tensile strength of the ESO plasticized blends were comparable with the DOP plasticized ones, but the elongation at break (EB) of the ESO blends fell short of that of the DOP blends. Also the retention of both tensile properties for the ESO blends was poorer than for DOP blends. Hardening and embrittlement also occurred in the ESO blends. Despite these weaknesses, ESO could be an ideal plasticizer for the PVC/ENR system as indicated by plasticizer permanence and the greater efficiency of plasticization. © 1998 SCI.     

不同硫化助剂对EPDM/MVQ共混物性能的影响

研究了PDM和TAIC两种助硫化剂对共混胶性能的影响。实验结果表明,随着TAIC用量的增加,共混胶的硫化速度和硫化程度先增加后减小;随着PDM用量的增加,共混胶的硫化速度变化不大,说明PDM反应不是很剧烈,但交联程度是一直增加的。随着硫化助剂用量增加,TAIC共混胶的拉伸强度、拉断伸长率和撕裂强度均大于PDM共混胶,而压缩永久变形的变化率正好相反。老化后共混胶的硬度、拉伸强度和100%定伸应力均增加,但是拉断伸长率降低。说明在老化过程中胶料发生了二次硫化现象,交联程度进一步完善,交联网络的分布更加均匀,交联密度进一步增加。用平衡溶胀法测试共混物的交联密度,表明TAIC共混胶的交联程度大于PDM共混胶。     

Reactive processing of ethylene-vinyl acetate rubber/polyamide blends via a dynamic transesterification reaction

Dynamic vulcanization process of ethylene-vinyl acetate rubber (EVM) and ternary polyamide copolymer (tPA) blends in the presence of tetraethyloxysilane (TEOS) was investigated. The morphology, crosslink density and mechanical properties of the resultant EVM/tPA thermoplastic elastomers (TPEs) were characterized. The dynamically crosslinked EVM phase was distributed homogeneously in the continuous tPA phase for the EVM/tPA (70/30) TPE, and the phase size of EVM decreased further as the TEOS content increased. The crosslink density reached 3.17 × 10^?5 mol cm^?3, and the tensile strength and the elongation at break were up to 10.6 MPa and 296 %, respectively, when the TEOS content was increased to 8 phr, and the heat oil resistance was accordingly enhanced. As compared to dicumyl peroxide-initiated crosslinking reaction of EVM, the crosslinking reaction of EVM through the transesterification reaction between EVM and TEOS presented lower crosslinking rate constant and activation energy, indicating that the transesterification reaction is more suitable for high temperature dynamic vulcanization processing. The optimized dynamic vulcanization process of EVM/tPA TPEs is useful for developing high-performance TPEs for automotive applications.     

Rheological and mechanical properties of dynamically cured poly(vinyl chloride)/nitrile butadiene rubber thermoplastic elastomers

Plasticized poly(vinyl chloride)/nitrile butadiene rubber (PVC/NBR) thermoplastic elastomers (TPEs) were dynamically cured in the melt stage with the incorporation of a semi‐efficient curing system using a Brabender Plasticorder at 150 °C and rotor speed of 50 rev min^?1. Sulfur concentration was progressively increased from zero to 1 part per hundred NBR to study the effect of dynamic curing on mechanical and rheological behaviour of the TPEs. The compounds were characterized in respect of their rheological and mechanical properties. The effectiveness of dynamic curing was studied using Brabender plastograms, a moving disc rheometer and swelling index measurement. The mechanical properties investigated include tensile strength, elongation at break, modulus at 100% elongation, tear strength and hardness. The influence of thermooxidative ageing on the mechanical properties was investigated by incubating the PVC/NBR TPEs in an air oven at 80 °C for 168 h. The torque values obtained from both rheometers increased with increasing sulfur dosage, while the swelling index decreased. The significant increase in the degree of curing evidenced by the steady reduction in the swelling index provided excellent proof of the efficiency of the dynamic curing technique. Thermo‐oxidative ageing resulted in a pronounced enhancement in mechanical properties as a function of sulfur content. This observation seems to indicate that some microstructural changes, such as the formation of new crosslinks, occur in the thermo‐oxidatively aged TPEs. This trend was supported by further reduction in the swelling index of the aged TPEs. © 2003 Society of Chemical Industry     

Nanomodified fillers in chloroprene‐rubber‐compatibilized natural rubber/acrylonitrile–butadiene rubber blends

Because of the structural dissimilarity, natural rubber (NR) and acrylonitrile–butadiene rubber (NBR) are immiscible, and compatibilizers are used during their blending. Neoprene or chloroprene rubber (CR) has a polar chlorine part and a nonpolar hydrocarbon part. Also, it has many advantageous properties, such as oil resistance, toughness, a dynamic flex life, and adhesion capacity. Hence, it is not less scientific to use CR as a compatibilizer in the blending of NBR with NR. Because many fewer studies on the use of neoprene as a compatibilizer in NR–NBR blend preparation are available, efforts were made to prepare 20:80 NR–NBR blends with CR with the aim of studying the effect of poly(ethylene oxide) (PEO)‐coated nano calcium silicate along with nano N‐benzylimine aminothioformamide and stearic acid coated nano zinc oxide in the sulfur vulcanization of the blends. The optimum dosage of the compatibilizer was derived by the determination of the tensile properties, tear resistance, abrasion resistance, compressions set, and swelling values. The tensile strength, tear resistance, and abrasion resistance of the gum vulcanizates of the blend were improved by the compatibilizing action of CR up to 5 parts per hundred parts of rubber (phr). In the case of the filled vulcanizates, the tear resistance, 300% modulus, hardness, and abrasion resistance increased with increasing dosage of nano calcium silicate. The elongation at break percentage decreased as expected when there was an increase in the modulus. Scanning electron microscopy was used to study the phase morphology of the blends. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012