Sulfonation of metallocene‐based polyolefinic elastomers and its influence on physicomechanical properties: Effect of reaction parameters,styrene grafting,and pendant chain length

Direct sulfonation and styrene‐mediated sulfonation were carried out onto metallocene‐based poly(ethylene‐co‐octene) (POE) and poly(ethylene‐co‐butene) (PBE) elastomers to impart polarity on the completely nonpolar rubbery matrices and to prepare a new class of elastomer. The influence of styrene‐grafting and pendant chain length on the degree of sulfonation was also studied. The effects of sulfonation, styrene grafting and styrene‐mediated sulfonation at their optimized levels on various physicomechanical properties were thoroughly investigated, and the resultant properties were correlated with structures of the modified elastomers. Higher extent of sulfonic acid groups were introduced through direct sulfonation in comparison with the styrene‐mediated sulfonation, whereas better thermal and mechanical properties were obtained through styrene‐mediated sulfonation in comparison with the direct sulfonation process. PBE had shown higher degree of sulfonation and percentage grafting than POE. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 8023–8040, 2008     

凹凸棒石/硅橡胶复合材料的热氧化降解和老化性能研究

本文采用高压均质结合对辊挤压工艺对天然凹凸棒石进行棒晶解离得到了纯度较高和比表面积较大(133.7 m²/g)的纳米解离凹凸棒石. 进一步通过机械共混法分别将天然凹凸棒石和纳米解离凹凸棒石与硅橡胶生胶复合制备了天然凹凸棒石-硅橡胶和纳米解离凹凸棒石-硅橡胶材料,研究了天然凹凸棒石和纳米解离凹凸棒石对凹凸棒石/硅橡胶复合材料热氧化降解和老化性能的影响. 结果表明,天然凹凸棒石-硅橡胶和纳米解离凹凸棒石-硅橡胶在300 oC热氧老化处理0.5 h后,相比于纯硅橡胶,初始5%失重温度从385 oC提高至396∽399 oC. 系列表征结果表明,天然凹凸棒石和纳米解离凹凸棒石增强了纳米粒子与硅橡胶之间的相互作用从而抑制了纳米颗粒聚集,并且可显著提高硅橡胶侧链Si-CH₃的保存率,从而提高了该复合材料的热氧化降解和老化性能. 此外,纳米解离凹凸棒石可大大抑制纳米粒子的长大;因此老化后,纳米解离凹凸棒石-硅橡胶表现出了比硅橡胶(10.6%、7.4%和5.0%)更高的拉伸强度、断裂伸长率和撕裂强度保留率(40.6%、34.9% 和30.1%).     

基于核磁共振技术探讨有机硅电解质物化特性

有机硅化合物是电解质材料研究的热点之一,其物理化学特性是衡量电池性能的重要参数.本文采用多种核磁共振（NMR）技术（包括¹H NMR、¹³C NMR、DOSY、⁷Li NMR、¹⁹F NMR）对有机硅化合物CN（CH₂）₂SiCH₃（OCH₂CH₂OCH₃）₂（BNS）的结构,电解液（LiPF₆/BNS）的溶剂化效应、扩散系数和热稳定性四个方面进行了分析评价,发现BNS和LiPF₆之间具有溶剂化效应;BNS的氰基（CN）和醚键（-O-）基团可与Li⁺形成络合物,且氰基配位能力优于醚键,络合键的形成促进了LiPF₆的离解和扩散,同时也提高了LiPF₆/BNS的热稳定性,证明高温下LiPF₆的分解是电解液失败的主要原因.该研究为开发新型电解质化合物及促进其性能提升提供了理论依据.     

Effect of cold plasma process on the surface wettability of NBR and the kerosene resistance of NBR/PTFE composites

In this study, first the acrylonitrile‐butadiene rubber (NBR5080) was modified by argon (Ar), air, and oxygen plasma at low temperature, and the effect of plasma process (power, time, and pressure) on the surface properties of NBR5080, the interfacial properties, physical properties, and the mechanical properties of NBR5080/polytetrafluoroethylene (PTFE) composites were investigated. The state contact angle and the surface free energy were applied to characterize the surface wettability of NBR5080. The scanning electron microscope and the atomic force microscope were used to observe the surface morphology of the NBR5080. The chemical changes on the NBR5080 surface were verified by X‐ray photoelectron spectroscopy. The average water contact angle the NBR5080 declined obviously when NBR5080 was treated by Ar (100 W/600 s/30 Pa). The active oxygen groups were introduced onto the surface of NBR5080 by cold plasma treatment and more active group containing oxygen were observed on the samples treated by Ar plasma. The peel strength between the NBR5080 and the PTFE was increased obviously, which increased from 0 to 44.2 N?m^?1 for Ar plasma treatment. The mass and the dimension of NBR5080 increase sharply after immersing in kerosene, whereas the NBR5080/PTFE composites changed a little. The mechanical properties of NBR5080 and NBR5080/PTFE composites decreased as the immersion time in kerosene increased, but the decreased degree of NBR5080 is higher than NBR5080/PTFE composites.     

Parabola-Hyperbola P-H kinetic model for NR sulphur vulcanization

A Parabola-Hyperbola (P-H) kinetic model for NR sulphur vulcanization is presented. The idea originates from the fitting composite Parabola-Parabola-Hyperbola (P-P-H) function used by the authors in [1,2] to approximate experimental rheometer curves with the knowledge of a few key parameters of vulcanization, such as the scorch point, initial vulcanization rate, 90% of vulcanization, maximum point and reversion percentage. After proper normalization of experimental data (i.e. excluding induction and normalizing against maximum torque), the P-P-H model reduces to the discussed P-H composite function, which is linked to the kinetic scheme originally proposed by Han and co-workers [3]. Typically, it is characterized by three kinetic constants, where classically the first two describe incipient curing and stable/instable crosslinks and the last reproduces reversion.The powerfulness of the proposed approach stands into the very reduced number of input parameters required to accurately fit normalized experimental data (i.e. rate of vulcanization at scorch, vulcanization at 90%, maximum point and reversion percentage), and the translation of a mere geometric data-fitting into a kinetic model. Kinetic constants knowledge from simple geometric fitting allows characterizing rubber curing also at temperature different from those experimentally tested.The P-H model can be applied also in the so-called backward direction, i.e. assuming Han's kinetic constants known from other models and deriving the geometric fitting parameters as result.Some existing experimental data available, relying into rheometer curves conducted at 5 different temperatures on the same rubber blend are used to benchmark the P-H kinetic approach proposed, in both backward and forward direction. Very good agreement with previously presented kinetic approaches and experimental data is observed.     

Viscoelastic behaviour of silica filled natural rubber composites – Correlation of shear with elongational testing

Dynamic mechanical behaviour of natural rubber-silica composites was studied by a frequency sweep method at different temperatures (40 °C,70 °C and 100 °C) using a dynamic mechanical analyzer and a rotorless rheometer, RPA, in an attempt to establish a correlation between the two. The composites with silica content up to 40 phr were studied. It was found that the dependence of dynamic modulus on the frequency as obtained from both the instruments followed a similar trend. This suggests that the dynamic mechanical properties of rubber compounds can be determined even during curing. A correlation could be arrived at between the two sets of data, making it possible to predict one set knowing the other. The impact of silane coupling agent, bis (3-triethoxysilylpropyl tetrasulphide), TESPT, on viscoelasticity was also investigated. The mechanical properties were improved in the presence of TESPT. Additionally, an increase in thermal stability was also observed in the presence of TESPT. Scanning electron micrographs showed the better filler dispersion in the case of silane-coupled silica composites.     

Comparative study on degradation of ethylene-propylene rubber for nuclear cables from gamma and beta irradiation

Considering safety is the priority concern of nuclear power plants, equipment qualification testing of the nuclear components manufactured should be paid special attention to. Thereinto, equivalent conversion (1:1) from the absorbed beta doses to gamma doses is a rule of thumb for irradiation qualification testing of the polymers used as nuclear cables, however whether it is reasonable and applicable to Chinese domestic polymers still requires investigation. In this paper, both gamma and beta irradiation testing with the actual dose rates and total absorbed doses in China Advanced Passive (CAP) series nuclear power plant was performed upon one domestically manufactured ethylene-propylene rubber intended for nuclear cable insulation in China. The mechanical and the electrical properties before and after irradiation were measured to compare the extent and the trend of degradation between the two irradiation types, and related oxidation degradation mechanism especially its attenuation along the thickness was quantitatively addressed.     

Understanding the effect of filler shape induced immobilized rubber on the interfacial and mechanical strength of rubber composites

Styrene butadiene rubber (SBR) composites with silica, halloysite nanotubes (HNTs) and montmorillonite (MMT) were prepared and the interfacial and mechanical properties were compared to understand the reinforcing behaviours of these fillers based on the results of SEM, DSC, DMA, etc. Due to the formation of interparticle domain, HNTs immobilized more rubber approaching their surface than silica and MMT. Interestingly, only tightly immobilized rubber chains made contribution to the enhancement of interfacial and mechanical strength of SBR composites. This was because the tightly immobilized rubber acted as a bridge in the filler-rubber interface and induced the formation of stretched rubber chains linked filler network when the composites were loaded in tension, while loosely immobilized rubber were easy to slip off from filler surface, causing the separation between filler and bulk rubber. Therefore, silica with more tightly immobilized rubber approaching its surface showed better reinforcing effect on rubber than HNTs and MMT.     

Interrelationship between total volatile organic compounds emissions,structure and properties of natural rubber/polycaprolactone bio-blends cross-linked with peroxides

Natural rubber/polycaprolactone (NR/PCL) bio-based blends with different organic peroxides were prepared using an internal batch mixer and subsequently cross-linked at 170 °C. Two types of commonly used organic peroxides, dicumyl peroxide and di(tert-butylperoxyisopropyl)benzene peroxide, were applied as free-radical initiator. Cross-linking efficiency of NR/PCL blends were investigated using oscillating disc rheometer measurements, followed by infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis and tensile testing. Total volatile organic compounds (TVOCs) emissions were determined using headspace analysis integrated with gas chromatography with flame ionization detector. Determined TVOCs emissions varying in range 21.6–52.1 μg/g and generally value of this parameter decreased with increasing content of PCL phase in studied blends or with application of more efficient di(tert-butylperoxyisopropyl)benzene peroxide as cross-linking agent. It was found that increasing of TVOCs parameter indicated deterioration of mechanical properties of NR/PCL blends, which corresponded with the changes in chemical structure and thermal properties of cross-linked NR/PCL. This confirms that evaluation of TVOCs parameter is interesting alternative for “conventional methods” to characterization of the studied bio-based blends.     

Application of fractional calculus methods to asymmetric dynamical response of CB-Filled rubber

Frequency-sweep tests at various temperatures were conducted to study the asymmetric dynamic response of carbon black (CB) filled rubber. The master curves of storage modulus were constructed by use of time-temperature superposition (TTS), and the dynamic response of the material over a wide range of frequencies covering about 20 decades exhibits asymmetry. Based on the experimental results, the fractional Zener model and Prony series are verified to be unsuitable to reproduce the dynamicviscoelastic behavior. Therefore, a modified model by adding a spring-pot into the fractional Zener model is presented. The applicability of the modified model in describing the dynamic behavior of the CB-filled rubber is validated by the experimental results.