Studies on novel binary accelerator system in sulfur vulcanization of natural rubber

The synergistic activity of binary accelerator systems in rubber vulcanization is well known. Binary accelerator systems are being widely used in industry and are becoming increasingly popular because of the fact that such mixed systems can effectively prevent prevulcanization, permit the vulcanization to be carried out at a lower temperature in a shorter time, and produce a vulcanizate with superior mechanical properties compared to those of a stock cured with a single accelerator. Thiourea and its derivatives are important secondary accelerators in this context. It is suggested that thiourea containing binary accelerator systems cause rubber vulcanization to proceed by a nucleophilic reaction mechanism. In the present study 1‐phenyl‐5‐ortho, ‐meta, and ‐para‐tolyl derivatives of 2,4‐dithiobiurets, which are more nucleophilic than thiourea and vary in their nucleophilic reactivity, are used as secondary accelerators along with 2‐morpholinothiobenzothiazole in the vulcanization of natural rubber. The results show an appreciable reduction in the cure time for the mixes containing the dithiobiurets compared to the reference mix. These results are indicative of a nucleophilic reaction mechanism in the vulcanization reaction under consideration. These vulcanizates also demonstrate comparatively better tensile properties and good retention of these properties after aging. An attempt is also made to correlate the variation in physical properties to chemical crosslink formation in the various vulcanizates. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3173–3182, 2003     

Effect of various efficient vulcanization cure systems on the compression set of a nitrile rubber filled with different fillers

Effect of various efficient vulcanization (EV) sulfur cure systems on the compression set of a nitrile rubber filled with carbon black and silica/silane fillers was examined. The cure systems had different amounts of thiuram and sulfenamide accelerators and elemental sulfur, whilst the loading of zinc oxide and stearic acid activators was kept constant. The fillers had surface areas from 35 to 175 m²/g. In this study, the lowest compression set was measured for the rubber filled with carbon black with 78 m²/g surface area, which was cured with an EV cure system made of a small amount of elemental sulfur and large amounts of the two accelerators. Interestingly, a small change in the amount of elemental sulfur had a bigger effect on the compression set than did large changes in the loading of the accelerators in the cure system. Among the fillers, carbon black caused less compression set of the rubber vulcanizate than the silica/silane system did. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41512.     

Dynamically vulcanized nitrile rubber/polypropylene thermoplastic elastomers

A new compatibilized method was used to prepare thermoplastic elastomer (TPE) of nitrile rubber (NBR) and polypropylene (PP) with excellent mechanical properties by dynamic vulcanization. Glycidyl methacrylate (GMA) grafted PP/amino‐compound was used as a compatibilizer. The effects of the curing systems, compatibilizer, PP type, and reprocessing on the mechanical properties of NBR/PP thermoplastic elastomers were investigated in detail. Experimental results showed that the addition of amino‐compound in the compatibilzer can significantly increase the mechanical properties of the NBR/PP thermoplastic elastomer. Compared with other amino‐compounds, diethylenetriamine (DETA) has the best effect. PP with higher molecular weight is more suitable for preparing NBR/PP thermoplastic elastomer with high tensile strength and high elongation at break. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2862–2866, 2002     

Ionic elastomers based on carboxylated nitrile rubber and magnesium oxide

The crosslinking of carboxylated nitrile rubber (XNBR) with magnesium oxide (MgO) leads to an ionic elastomer with thermoplastic nature and better physical properties than the ones obtained with other metallic oxides. The crosslinking reaction leads to the formation of a metallic salt as unique product, as it could be seen on the ATR analysis of the samples, prepared at different reaction times. The mechanical properties of the material increase with the amount of crosslinking agent and segregation of an ionic microphase takes place. The presence of this microphase is demonstrated by a relaxation at high temperatures. The apparent activation energy of this relaxation is smaller than the activation energy of the glass transition of the elastomer, the former being more dependent on the amount of metallic oxide than is the latter. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1894–1899, 2007     

Effect of network heterogeneities on the physical properties of nitrile rubbers cured with dicumyl peroxide

The scope of this study is to continue our earlier studies on the peroxide curing of diene elastomers. The effect of peroxide content and temperature on the curing and mechanical properties of NBR and H‐NBR rubbers with different acrilonitrile content was evaluated. Experimental evidence indicates that saturated rubbers behave as expected whereas in unsaturated nitrile rubbers abstraction of allylic hydrogen and addition to the double bonds can act as mechanism of crosslinking, the weight of each mechanism is dependent of DCP content and curing temperature. The addition mechanism produces densely crosslinked zones or clusters, generating a heterogeneous network with effect on the vulcanizate properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3377–3382, 2007     

Studies on double networks in natural rubber vulcanizates

The concept of double networks is a rather new idea, by which one imparts chain orientation in elastomers. Double networks were made in natural rubber vulcanizates cured with a single and a new binary accelerator system. Double networks with different extensions were prepared and their effects on tensile properties were analyzed. The influence of extent of initial cure on double‐network formation was examined. Thermal stability of the double network formed was analyzed by ageing of the double networks and was found to improve with residual extension. Crosslink density of the networks formed was determined by swelling methods and stress–strain analysis. It was found that crosslink density increased with double‐network formation and residual extension. The stress–strain behavior and moduli were analyzed to study the effect of these properties on double‐network formation. Double networks were hardly affected by the binary accelerator system. Based on the studies it was found that residual extension was the major factor determining the final properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1068–1076, 2004     

Vulcanization of carboxylated nitrile rubber (XNBR) by a mixed zinc peroxide–sulphur system

Vulcanization of carboxylated nitrile rubber (XNBR) with a mixed system based on zinc peroxide and sulphur accelerators produces materials with favourable mechanical properties because of the formation of ionic aggregates which give the vulcanized compounds a certain rigidity. These properties are drastically reduced by the effect of saturated ammonia vapour which plasticizes the ionic aggregates. This plasticization, however, is reversible and the aggregates can be regenerated by addition of a solvent, which results in recovery and even improvement of the original properties such as stress at constant deformation, tensile strength, crosslinking density and storage modulus. The temperatures of the two transitions observed in the relaxation spectra, the glass transition of the polymer and the ionic transition corresponding to ionic aggregates, are displaced to higher values when ionic structures are regenerated. © 2000 Society of Chemical Industry     

Vulcanization of carboxylated nitrile rubber (XNBR) by zinc peroxide

The vulcanization of carboxylated nitrile rubber (XNBR) with zinc peroxide, which produces ionic crosslinks, has been studied in relation to vulcanization time. Vulcanized compounds present two transitions, corresponding to the glass transition of the polymer at low temperatures and the ionic transition resulting from the formation of ionic aggregates. Both transitions are displaced to higher temperatures with increasing crosslink density. The ionic associations which give rise to high values of mechanical properties disappear on exposure of the vulcanized compounds to saturated ammonia vapour. This treatment produces a decreased crosslink density resulting in the disappearance of the ionic transition. When the action of ammonia is terminated by immersion in solvent followed by drying, the original crosslink density is recovered and the ionic transition reappears, although at higher temperatures. However, with increasing crosslink density, the difference between the temperatures at which both transitions take place diminishes. All these factors can be interpreted as reflecting the generation of a new and more compatible arrangement of the newly-appearing ionic clusters. © 1999 Society of Chemical Industry     

The behavior of dithiocarbimate derivative as safety accelerator of natural rubber compounds

A conventional vulcanization system containing tetrabutylammonium bis(4‐methylphenyldithiocarbimato)zincate(II) (ZNIBU) was used for curing of natural rubber (NR) compounds. Rheometric (t_s1, t₉₀, and CRI) and mechanical properties, such as tensile and tear strengths and modulus at 300%, were measured to evaluate the acceleration potential of ZNIBU. Commercial accelerators (TMTD, MBTS, and CBS) and a binary system CBS/ZNIBU were also tested for comparison purposes. It was observed that ZNIBU alone does not give either safe scorch time or cure rates appropriate for industrial applications. Nevertheless, mechanical properties are comparable to those given by the other accelerators used. As for the binary system, positive synergistic effects can be found in tear strength and modulus of NR vulcanizates. Besides, ZNIBU does not contribute for the formation of nitrosamines in the vulcanization process. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Failure properties of thermoplastic elastomers from polyethylene/nitrile rubber blends: Effect of blend ratio,dynamic vulcanization,and filler incorporation

Thermoplastic elastomers from blends of high‐density polyethylene and acrylonitrile butadiene rubber were prepared by a melt‐blending technique. The blends were dynamically vulcanized using sulfur, peroxide, and mixed curing systems. The peroxide concentration was varied to obtain samples of varying degrees of crosslinking. The peroxide system showed better mechanical properties. The crosslink density determination by the equilibrium swelling method revealed that the enhancement in properties can be correlated to the extent of crosslinking. It is observed that the effect of dynamic vulcanization on the property improvement is much more pronounced in rubber‐rich blends. To study the effect of filler incorporation on mechanical properties, fillers such as carbon black, silica, silane‐treated silica, and cork‐filled samples were prepared. All filled systems, except cork filled, exhibited superior mechanical properties. Scanning electron micrographs of selected fractured surfaces were analyzed to study the failure mechanism of the different compositions. Various theoretical models were applied to correlate the observed mechanical behavior with that of theoretically predicted values. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2912–2929, 2006     

Effect of zinc oxide nanoparticles as cure activator on the properties of natural rubber and nitrile rubber

Zinc oxide (ZnO) nanoparticles were synthesized by homogeneous precipitation and calcination method and were then characterized by transmission electron microscopy and X‐ray diffraction analysis. Synthesized ZnO was found to have no impurity and had a dimension ranging from 30–70 nm with an average of 50 nm. The effect of these ZnO nanoparticles as cure activator was studied for the first time in natural rubber (NR) and nitrile rubber (NBR) and compared with conventional rubber grade ZnO with special reference to mechanical and dynamic mechanical properties. From the rheograph, the maximum torque value was found to increase for both NR and NBR compounds containing ZnO nanoparticles. ZnO nanoparticles were found to be more uniformly dispersed in the rubber matrix in comparison with the conventional rubber grade ZnO as evident from scanning electron microscopy/X‐ray dot mapping analysis. The tensile strength was observed to improve by 80% for NR when ZnO nanoparticles were used as cure activator instead of conventional rubber grade ZnO. An improvement of 70% was observed in the case of NBR. The glass transition temperature (T_g) showed a positive shift by 6°C for both NR and NBR nanocomposites, which indicated an increase in crosslinking density. The swelling ratio was found to decrease in the case of both NR and NBR, and volume fraction of rubber in swollen gel was observed to increase, which supported the improvement in mechanical and dynamic mechanical properties. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Effect of the network topology on the tensile strength of natural rubber vulcanizate at elevated temperature

The influence of network topology on tensile strength at elevated temperature of natural rubber compounds vulcanized with different systems was studied. The tensile strength behavior of natural rubber at high strain is attributed to the capacity to crystallize on stretching. Variation of this property with the temperature and/or crosslink density was related, not only with the nature of the crosslinks, but also with their spatial distribution. In this sense, measurements of the freezing point depression of cyclohexane imbibed in the rubber matrix were used to evaluate the spatial distribution of the crosslinks. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1219–1223, 2005     

促进剂M-La的合成及对天然橡胶的硫化促进作用

采用沉淀法用对氨基苯甲酸、氢氧化钠和硝酸镧在乙醇环境下合成了促进剂对氨基苯甲酸镧(M-La),研究了其对天然橡胶硫化的促进作用。通过红外光谱分析、热分析和元素分析等确定所合成促进剂M-La的分子式为La(C_7 H_6 NO_2)_3·2 H_2O。硫化性能测试结果表明,随着促进剂M-La用量的增加,天然橡胶的硫化速率指数由139增加至227,焦烧时间逐渐延长而正硫化时间基本维持不变,硫化胶的加工安全性不断增强;硫化胶交联密度由最初的1.95×10~(-4) mol/g逐渐增大至2.41×10~(-4) mol/g。促进剂M-La对天然橡胶硫化的促进作用比较明显。     

Oil resistance and low-temperature characteristics of plasticized nitrile butadiene rubber compounds

The mechanical properties and oil resistance of nitrile butadiene rubber as an automotive material are investigated under low-temperature conditions. We discuss the effects of various plasticizers, such as dioctyl adipate, adipic acid ester, polyether ester, and adipic acid polyester. The mechanical properties after thermal oxidation aging, as well as oil resistance and low-temperature characteristics of the compounds, are measured using a moving die rheometer, universal testing machine, differential scanning calorimeter, low-temperature retraction tester, and gehman torsional stiffness tester. We focus on how the oil resistance and low-temperature characteristics are affected by the plasticizer type and plasticizer content. The results demonstrate that nitrile butadiene rubber compounds are affected by the low molecular weight and viscosity of the plasticizer. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47851.     

Vulcanization characteristics and mechanical properties of nitrile rubber filled with short leather fibres

Leather shavings have been used as filler in short fibre form for nitrile rubber reinforcement. Shavings neutralized with sodium bicarbonate and ammonia showed improved vulcanization characteristics and mechanical properties, whereas sodium hydroxide neutralized shavings exhibited poor properties. Swelling of the vulcanizates in water and 1% NaOH was found to increase with leather loading, whereas in MEK a reversed trend was observed. Thermogravimetric analysis indicates that the thermal stabilities of the vulcanizates fall between those of pure leather and gum nitrile rubber vulcanizate.     

Effect of nano zinc oxide on the cure characteristics and mechanical properties of the silica‐filled natural rubber/butadiene rubber compounds

With the increasing interest in environmental and health issues, legal restrictions, such as European Union (EU) End of Life Vehicle Directives, were strengthened. This led us to incorporate nano zinc oxide (nano‐ZnO), with particle sizes of 30–40 nm and specific surface areas of 25.0–50.0 m²/g, instead of conventional ZnO into natural rubber (NR)/butadiene rubber (BR) compounds to decrease the content of zinc in the formulation. In the unfilled system, only a 20 wt % nano‐ZnO content, compared to conventional zinc oxide content, showed the cure characteristics and mechanical properties of the same level. This was because the increase in the specific surface area of the nano‐ZnO led to an increase in the degree of crosslinking. The effect of nano‐ZnO on the cure characteristics and mechanical properties was more pronounced in the silica‐filled system than in the unfilled system. This was mainly because of the dispersing agent used in the silica‐filled system, which also improved the dispersion of nano‐ZnO. The silica‐filled NR/BR compounds containing 0.3–3.0 phr of nano‐ZnO showed improved curing characteristics and mechanical properties, such as optimum cure time, 100 and 300% modulus, tensile strength, and tear strength compared to the compound with 5 phr of conventional ZnO. The optimum amounts of nano‐ZnO and stearic acid were only 1.0 and 0.1 phr, respectively. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Physical,mechanical, and viscoelastic properties of natural rubber vulcanizates cured with new binary accelerator system

Natural rubber was vulcanized with a new binary accelerator system based on 1‐phenyl‐2,4‐dithiobiuret (DTB) and dicyclohexyl benzothiazyl sulfenamide. A significant reduction in cure time was observed with the addition of DTB. The cure kinetics was investigated and the activation energy was determined. The mechanical properties were improved by adding DTB, and the maximum values are shown at an optimum concentration. Estimates of the concentration of crosslinks and of the relative proportions of different types of crosslinks were made by the chemical characterization of the vulcanizates. The crosslink densities obtained from swelling measurements and stress–strain measurements were compared with those obtained from modulus measurements. All of them follow a similar trend and support the observed mechanical properties. A dynamic mechanical analysis of the mixes was carried out and the activation energy was determined from Arrhenius plots. The glass‐transition temperature was found to increase with the increase in crosslink density and frequency of measurements. The stress–strain curves were found to not deviate from the strain crystallizing nature of natural rubber. The mechanical properties, network characterization, and processing characteristics were used to optimize the DTB concentration. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2193–2203, 2003     

Effect of ammonium derivatives of oligoamidephosphates on the vulcanization characteristics and mechanical properties of some rubber compounds. 1. Isoprene rubber compounds

IR compounds containing ammonium derivatives of oligoamidephosphates were studied with respect to vulcanization and mechanical characteristics. The ammonium derivatives were obtained as neutral analogues of the corresponding oligoamidephophates. The results indicate an improved efficiency of the neutral products and the possibility of a partial replacement of traditional sulphenamide accelerators with the studied ammonium derivatives, leading to a strong improvement of the fatigue resistance (by more than one order). The addition of such products without reducing the level of the basic accelerator led to additional acceleration—the cure rate increased and the cure time decreased up to three times. Ageing resistance showed a tendency to improve.     

原油对丁腈橡胶密封件性能的影响

以原油为试验介质,模拟井况研究原油对丁腈橡胶密封件性能的影响。结果表明,在模拟井况条件下,丁腈橡胶密封件出现老化现象,随着浸泡时间的延长,密封件的拉伸强度和扯断伸长率逐渐下降,硬度逐渐增大,老化机理以分子链交联老化反应为主;随着温度的升高,老化速率快速增大;高含水率的原油对丁腈橡胶密封件的性能存在负面影响。     

液体低分子聚异戊二烯改性丁腈橡胶发泡材料

借助核磁共振技术研究了中丙烯腈含量（丙烯腈含量约33%）的4个牌号丁腈橡胶（NBR）的微观结构对NBR硫化速度的影响,以此探索提高NBR硫化速度的方法。结果表明,在NBR分子链中存在着三种微观结构,即顺式1,4-、反式1,4-和乙烯基结构,其中乙烯基结构的含量与NBR的硫化速度有关联的规律性,乙烯基结构含量高则NBR硫化速度快。低分子液体聚异戊二烯（LLPI）作为NBR的改性剂提高了NBR的硫化速度,当添加5份LLPI时,正硫化时间比未添加缩短了约2.5min;LLPI也改善了NBR的加工性能,降低了胶料的门尼黏度;还提升了发泡材料的力学性能,添加5份LLPI的发泡材料拉伸强度增大了14.2%,拉断伸长率减小了27.1%,并且可以与NBR形成交联网络并提高交联结构紧密性,降低胶料的熔体强度,使发泡材料的泡孔生长良好。