New binary accelerator systems for sulphur vulcanisation of styrene butadiene rubber

Abstract

It is suggested that binary systems of rubber vulcanisation containing thiourea proceed by a nucleophilic reaction mechanism. The exact mechanism of the chemical reactions involved when binary accelerator systems are used in rubber vulcanisation is not fully understood even now. It differs with the systems and the nature of the elastomer used. In the present work, a derivative of thiourea, N-amidino N'-phenyl thiourea (APT), was studied as a secondary accelerator along with tetramethyl thiuram disulphide (TMTD)/mercaptobenzothiazyl disulphide (MBTS) in the sulphur vulcanisation of styrene butadiene rubber. Thiourea binary systems were used as controls. The binary systems containing APT are very effective in reducing the optimum vulcanisation time. APT being more nucleophilic than thiourea, is more reactive here (as observed by the reduction in cure time). A nucleophilic reaction mechanism is indicated in the vulcanisation reaction under review. Different concentrations of APT were tried in various mixes using standard recipes, and reference mixes were also evaluated. The optimum dosage of APT required has been derived based on the cure characteristics of the mixes and the physical properties of the vulcanisates.     

Preparation and characterization of exfoliated graphite and its styrene butadiene rubber nanocomposites

Nanocomposites consisting of styrene butadiene rubber (SBR) reinforced with the modified-graphite and natural-graphite with concentrations of 5 wt% were fabricated. Processing techniques such as acid treatment, thermal shock, sonication were employed in the fabrication of modified-graphite.The graphite platelets oxidized using sulfuric and nitric acids were analyzed by the Raman scattering, Fourier transformed infrared spectroscopy (FT-IR) and X-ray diffraction (XRD). The FT-IR results indicate the presence of acid groups in the treated samples, and Raman spectroscopy of acid-graphite platelets further corroborate the formation of surface defect due to the introduction of functional groups. However, the structure of XRD peaks did not change irrespective of processing techniques.The SBR-based nanocomposites were characterized using the scanning electron microscopy (SEM), rheometer, Instron tensile machine, thermal and electrical analyser.The results showed that nanocomposites onto acid-graphite platelets enhanced mechanical properties and fatigue properties of nanocomposites compared to those containing natural-graphite due to the increase in the interaction between the polymer and the modified-graphite. And the dynamic properties of nanocomposites had no influence according to the processing techniques. Also, thermal and electrical properties of nanocomposites using acid-graphite platelets were enhanced due to the broadened specific surface by the acid treatment.     

Tear and processing behaviour of short sisal fibre reinforced styrene butadiene rubber composites

The tear failure and processing characteristics of short sisal fibre reinforced styrene butadiene rubber (SBR) composites were investigated. Tear strength was examined with special reference to the effects of fibre length, fibre orientation, fibre concentration and bonding agent. It was observed that the tear strength depends on all the above factors. The tear failure mechanism was analysed from fractographs taken using a scanning electron microscope (SEM). During tear testing, the composites failed by a shearing process. Microscopic examination of cracks propagating in SBR composites revealed that the amorphous SBR matrix developed cracks, leaving ligaments of rubber attached to the broken fibres. The rubber particles were stretched as the crack opened and failure occurred at large critical extensions. It was observed that an increase in the concentration of fibres increased the tear strength in both longitudinal and transverse directions. The tear strength values were almost three to four times higher than those of the unfilled vulcanizates under similar conditions. In order to analyse the processing behaviour, the green strength, mill shrinkage and Mooney viscosity of the compounds were determined. Finally, the polymer–filler interaction was studied using the Lorenz–Park and Kraus equations.     

凝聚母液pH值的变化对环保型丁苯橡胶SBR1502E性能的影响

以中国石油吉林石化公司环保型丁苯橡胶SBR1502E为研究对象,研究了凝聚母液在不同pH值下对胶性能的影响.结果表明,在不改变母液温度、胶液进料量、高分子絮凝剂加入量情况下,凝聚母液pH值的变化对胶的性能产生较大影响,当初始pH值为3.0～3.5时,环保型丁苯橡胶SBR1502E的性能全部达到优级品技术标准.     

埃洛石纳米管对丁苯橡胶的增强作用

研究了未经表面改性和用双-[3-(三乙氧基硅)丙基]四硫化物(Sj-69)改性的埃洛石纳米管(HNTs)对丁苯橡胶(SBR)硫化胶力学性能的影响及其微观形貌.结果表明,HNTs对SBR具有明显的增强作用;Si-69能进一步提高其增强效果,有效地改善HN/s在橡胶基体中的分散,并能降低SBR/HN了s硫化胶的滚动阻力和动态生热.     

SMC晶须在丁苯橡胶中的应用

对硅镁钙晶须（SMC晶须）在丁苯橡胶（SBR）中的应用进行了研究,考察了晶须用量（0～50phr）对胶料的硫化特性和硫化胶的力学性能的影响,并与常用的填料白炭黑（WCB）和碳酸钙（CaCO3）进行了比较。实验结果表明：SMC晶须对SBR有促进硫化作用;SMC晶须对SBR具有一定的补强作用,拉伸强度随着晶须用量的增加而增大;用量相同时,SMC晶须填充的复合材料硬度和撕裂强度与WCB填充的相当,300%定伸应力比WCB填充的高,拉伸永久变形比WCB小得多;SMC晶须补强效果远优于CaCO3。     

Vulcanization kinetics of nano-silica filled styrene butadiene rubber

It was shown that the physical filler-polymer and filler–filler interactions, apart from the filler surface chemistry, has a substantial role in controlling the vulcanization kinetics of styrene butadiene rubber filled with nano-silica in a sulfur vulcanization system. Kinetic studies by the oscillating disc rheometer, differential scanning calorimeter, and swelling tests revealed that the vulcanization rate goes through a maximum as loading of silica increases, but conversion in crosslinking continuously decreases as the amount of silica increases. The effect of silica loadings on the vulcanization reactions was linked to the immobilization of rubber chains around particles as well as in a polymer-mediated filler network, which were differentiated by the nonlinear viscoelastic behavior of rubber vulcanizates. By surface modification of nano-silica, the accelerating/decelerating effects of nano-silica on the vulcanization reactions were altered corresponding to the non-linear viscoelastic behavior of the vulcanizates. Therefore, a mechanism was proposed which correlates vulcanization kinetics of rubber to the dynamics of chains influenced by the reinforcing fillers.     

丁苯橡胶生产及市场分析

综述了国内外丁苯橡胶的生产及市场情况,对国内丁苯橡胶的市场发展趋势进行了分析。此外,还对国内丁苯橡胶行业存在的不足提出了几点建议。     

Some considerations concerning the dynamic mechanical properties of cured styrene–butadiene rubber/polybutadiene blends

The dynamic mechanical response of several binary mixtures of a styrene–butadiene copolymer and high cis‐polybutadiene has been studied. The loss tangent and shear modulus were measured with a free damping torsion pendulum at temperatures between 143 and 343 K in argon atmosphere. From the loss tangent data the glass transition temperature of each sample was evaluated. The results can be represented by the Fox equation that relates the glass transition temperature of the blend with that of constituent polymers. The influence in the loss tangent data of the crystallization of the high cis BR used in the blend is discussed. A study of the separation of the crystalline and amorphous parts in the polybutadiene using the storage modulus data is presented. Finally, the loss of crystallinity at different contents of SBR in the blend is analysed using the dynamic mechanical data. © 2000 Society of Chemical Industry     

丁苯橡胶生产及市场分析

综述了国内外丁苯橡胶（SBR）的生产及市场情况,对国内SBR的市场发展趋势进行了分析。并预测在世界金融危机的影响下,国内SBR需求增长将会放缓,而国内产能的猛增,将加剧SBR产能过剩,造成供过于求的局面。此外,本文还对国内SBR行业存在的不足提出了几点建议。     

Adhesion of flame-treated polyolefins to styrene butadiene rubber

Samples of polyethylene and polypropylene have been submitted to repeated short duration (75 ms) flame treatments, at optimum flaming conditions. Surface energies of untreated and flamed specimens were determined by liquid contact angle measurements. It appears that the surface energy of polyethylene increases much more than that of polypropylene after flame treatment. The flamed polymer surfaces were further examined by electron spectroscopy, Fourier Transform IR spectroscopy and secondary ions mass spectrometry. The adhesion properties of modified polymer surfaces were studied by testing in peel the bonded Styrene Butadiene Rubber/polyolefins assemblies. Scanning electron microscopy (SEM) and water contact angle measurements have been used to observe the locus of failure. Good correlations were obtained between surface energy and adhesion strength, the increase in adhesion strength being particularly important for flamed PE/SBR assemblies. In addition, the peeling in a liquid medium allowed the determination of the respective contribution to adhesion of chemical and physical interactions. It is shown that a major part of the adhesion strength increase is of chemical origin, particularly for the bonded flamed PE/SBR assemblies.     

Effect of ingredients on the electrical conductivity of styrene butadiene rubber

The effect of different ingredients, which are usually added during the preparation of rubber mixtures, on the electrical conductivity σ of styrene-butadiene rubber (SBR-1502) has been studied. It was found that processing oil (as softener) showed a marked increase in σ with respect to the pure sample. Stearic acid (as antioxidant), however, did not show a considerable effect on σ. The addition of constant concentration of 50 phr from different types of carbon black (filler) namely, ISAF, HAF, FEF and SRF to the rubber matrix resulted in different values of the initial conductivity of the vulcanized samples. The conduction mechanism through carbon black-loaded rubber vulcanizates has been discussed and rough estimation of the separation distance between carbon black particles (or aggregates) suggested. The carbon black-loaded rubber vulcanizates showed a reasonable stability and reproducibility of σ after pre-thermal-oxidative ageing at 365 K for 30 days.     

溶聚丁苯胶F-1204的结构特性与应用

简述了溶聚丁苯胶的结构与性能的关系，总结了茂名溶聚丁苯胶F-1204在轮胎胎面胶、制鞋、胶管胶带应用中的特点，并提出了改善SSBRF-1204加工性能的措施。     

中结合苯乙烯含量丁苯橡胶在轮胎中的应用研究

考察了采用中结合苯乙烯含量丁苯橡胶SBR1756制备轮胎的流变性能、老化性能、抗湿滑性能、滚动阻力以及耐磨耗性能,并与SBR1723N制备的轮胎性能进行了对比。研究结果表明,采用SBR1756制备的轮胎抗湿滑性能和耐磨耗性能优于采用SBR1723N制备的轮胎,两者的滚动阻力相当。     

Molecular simulations of gas transport in nitrile rubber and styrene butadiene rubber

Nitrile rubber (NBR, 39:61 wt% of acrylonitrile:butadiene) and styrene butadiene rubber (SBR, 50:50 wt% of styrene:butadiene) matrices have been equilibrated by molecular dynamics (MD) simulations. Transition-state approach is used to calculate the diffusion and solubility coefficients of small penetrants in these matrices, indicating quite low values in NBR and reasonable agreement with experimental results. MD simulations have been performed to analyze water diffusion in these matrices. Aggregation of water molecules is observed in the hydrophobic matrix SBR. MD simulations with fictitious nonpolar water molecules inhibit aggregation and lead to enhanced diffusion in SBR. In NBR there is a slight increase in diffusion for fictitious water molecules. The lower diffusion constants in NBR result from slower local relaxation of the matrix due to tighter intermolecular packing and higher cohesive energy density. The free volume distribution that affects solubility coefficients is not a major determining factor for the diffusion coefficients in these matrices.     

丁苯嵌段共聚物的催化氢化研究进展

介绍了丁苯嵌段共聚物的催化加氢技术,综述了茂金属催化剂,环烷酸镍（钴）催化剂,三苯基膦-氯化钌（铑）,铁钴镍螯合物均相催化剂及非均相催化剂的技术进展。讨论了氢化丁苯嵌段共聚物氢化度的定性分析和定量分析方法。     

Effect of prevulcanization on the rheological behavior of natural rubber/styrene butadiene rubber latex blends

The effect of prevulcanization on the rheological behavior of natural rubber (NR), styrene butadiene rubber (SBR) latices, and their blends was studied with special reference to shear rate, blend ratio, vulcanizing systems, prevulcanization time, and accelerator systems. The NR latex showed a sharp increase in viscosity with increase in prevulcanization time due to high extent of crosslinking. However, SBR latex showed marginal effect on viscosity with prevulcanization time due to its low dry rubber content and low degree of unsaturation. Blends showed variations in viscosity according to the change in composition. The use of a single accelerator was found to have marked influence on the viscosity of the blends compared with a combination of accelerators. Swelling experiments were carried out in order to determine the crosslink density of the blends. The viscosity changes have been correlated with the crosslinking density of the latices and their blends. © 1996 John Wiley & Sons, Inc.     

橡胶助剂Silane-M对丁苯橡胶/白炭黑复合材料硫化性能的影响

用硫化仪考察了橡胶助剂3-苯并噻唑硫代-1-丙基-三乙氧基硅烷(Silane-M)对丁苯橡胶/白炭黑复合材料硫化性能的影响.结果表明,Silane-M可明显缩短丁苯橡胶/白炭黑复合材料的正硫化时间,但不影响其焦烧时间.Silane-M具有一定的促进作用,可以加快硫化速率.未添加和添加6份(质量)Silane-M的丁苯橡胶/白炭黑复合材料在135～160 ℃的硫化温度系数和硫化反应表观活化能均比较接近,2种复合材料的硫化性能对温度的依赖性基本一致.     

提高乳聚丁苯橡胶转化率的影响因素

以吉林石化公司生产的丁苯橡胶(1500)为研究对象,以12 h内聚合转化率达到(70±2)%、产品性能与转化率为(62±2)%者相当为目标,研究了引发剂、相对分子质量调节剂、电解质、单体配比与纯度及乳化剂等对丁苯橡胶聚合的影响,测定了不同转化率丁苯橡胶胶乳的机械稳定性及丁苯橡胶生胶和硫化胶的性能。结果表明,在不改变原材料品种和规格的前提下,于氧化剂用量110%(以标准配方所用质量为100%计,下同)、还原剂用量100%和助还原剂用量110%,硫醇初始量与补加量的质量比为100/20、补加时机在反应开始后2 h,电解质用量为110%~115%、初始时一次加入,丁二烯与苯乙烯的质量比为(72.0/28.0)~(72.5/27.5),乳化剂初始量与补加量的质量比为100/10、补加时机在反应开始后2 h的条件下,在12 h内可以使丁苯橡胶1500的聚合转化率提高到(70±2)%,并确保其产品性能全部达到国标优级品标准。