国内丁腈橡胶生产情况及市场分析

综述了国内外丁腈橡胶的生产及市场情况，对国内丁腈橡胶的市场发展趋势进行了分析和预测。并针对入世后国内丁腈橡胶行业存在的不足提出了几点建议。     

丁腈橡胶非均相催化加氢研究进展

丁腈橡胶（NBR）选择性催化加氢是制备高附加值、高性能氢化丁腈橡胶（HNBR）的一个重要过程。将链段中C==C双键加氢饱和而保留氰基基团,不仅可保持其原有的耐油性和耐磨性,而且可极大地改善其耐侯性、耐臭氧性等。本文介绍了NBR加氢的几种工艺,着重综述了NBR非均相催化加氢的研究进展及发展方向,探讨了负载型催化剂的载体孔道结构和表面性质及活性组分组成对NBR加氢性能的影响。本文还对非均相催化加氢过程中的溶剂效应、催化剂的回收和循环再生进行了阐述,提出溶剂对催化加氢速率和加氢度都有重要影响,溶剂的受氢能力（β值）是影响加氢过程的关键参数。催化剂失活的主要原因是表面活性位点被聚合物覆盖,而利用有效的溶剂洗涤或者采用催化剂表面功能化的方式,可促使活性位再次暴露,恢复其加氢活性。最后,对非均相加氢制备高附加值HNBR体系中的催化剂设计、溶剂效应和催化剂再生等发展方向进行了展望。     

共混比对丁腈橡胶/氯醚橡胶性能的影响

研究了共混比时常规共混及动态硫化共混丁腈橡胶(NBR)／氯醚橡胶(ECO)的力学性能及加工流变性能的影响。结果表明,共混比对NBR／ECO胶料的力学性能及加工流变性能影响显著。NBR经动态硫化后,压缩永久变形及挤出胀大明显减小,拉伸强度提高,表现黏度随ECO用量的增大而减小。共混比对常规共混胶的表观黏度影响不大。动态硫化有利于改善NBR／ECO胶料的加工性能。     

High‐performance hydrogenated nitrile butadiene rubber composites by in situ interfacial design of nanoclays

Considering industrial requests, it has become a hot issue to prepare advanced rubber composites with high strength and great toughness. Despite enhanced strength and stiffness, rubber composites suffer markedly reduced extensibility and toughness. Herein, a novel interfacial strategy is proposed to fabricate amine‐modified montmorillonite (MMT)/hydrogenated nitrile butadiene rubber composites by designing in situ ionic bond interfaces. The well‐distributed interfaces, which are composed of protonated amine groups on the MMT surfaces and electronegative methacrylic acid (MA), were constructed by adding a slurry with a small amount of MMT and MA to rubber. After the vulcanization, self‐polymerization of MA developed nanoparticles and grafting structures onto rubber chains to bond MMT by strong ion attractions. Although the crosslinking degree of rubber was reduced, the dispersion of MMT and its interfacial interactions with rubber were improved remarkably, as demonstrated by morphology observations, dynamic mechanical analysis and infrared spectra. As a result, the strength, modulus, elongation, toughness and gas barrier properties of the rubber composites were simultaneously strikingly improved relative to composites without MA modifiers. We believe that this work provides a promising methodology of fabricating high‐performance rubber composites. © 2019 Society of Chemical Industry     

丁腈橡胶非均相加氢催化剂失活原因及再生性能研究

对丁腈橡胶非均相催化加氢制备高附加值氢化丁腈橡胶过程中催化剂失活的原因进行了探究,发现造成催化剂活性下降的原因并不是贵金属纳米颗粒的流失、团聚或中毒,而是催化剂表面的活性位被聚合物覆盖而无法与反应物接触,因此将覆盖在活性位上的聚合物进行脱除才是催化剂再生和重复利用的关键。根据相似相容原理选择单溶剂或者混合溶剂对反应后催化剂进行处理,结果表明经过乙酸乙酯、丁酮、N,N-二甲基甲酰胺以及N-甲基吡咯烷酮这四种有机溶剂处理后,其催化加氢活性可以恢复至新鲜催化剂活性的90%;当用混合溶剂处理后,其催化活性可以提高至新鲜催化剂活性的95%,且循环利用4次其催化活性仍能保持不变。     

Effect of cyanide content on the tribological performance of nitrile butadiene rubber

Nitrile butadiene rubber (NBR) has received a lot of attention as a sealing material, and its tribological performance is a crucial factor in determining the efficiency with which it will operate under various operating situations. In this study, NBR specimens with varying degrees of cyanide content, namely low cyanide (DN401), medium cyanide (DN2850), medium-high cyanide (DN3380), and high cyanide (DN4050), were selected to investigate their tribological behavior when subjected to NO.10 aviation oil. To emulate their frictional responses during startup and shutdown operations, all four types of NBR were assessed under dry conditions. As the cyanide content increased, the coefficient of friction (COF) dropped from 1.381 to 0.810 and wear rate dropped from 2.38 × 10⁻³ mm³/(N m) to 1.88 × 10⁻⁴ mm³/(N m). When employed in conjunction with NO.10 aviation oil, DN401 and DN3380 exhibited COFs of 0.0963 and a slightly higher value of 0.127, respectively. Following aging treatment at 80°C in NO.10 aviation oil, stress reduction reached 65.8%, indicating the poorest performance among the four variants of NBR. Considering the COF, wear rate, and aging performance, DN3380 emerges as the most favorable choice for practical applications, thereby offering valuable insights into the selection of nitrile rubber for sealing materials.     

Investigation on the mechanical properties and oil resistance of sulfur cured nitrile rubber/hydrogenated nitrile butadiene rubber blends

Nitrile rubber (NBR)/hydrogenated nitrile butadiene rubber (HNBR) blends with various ratios were compounded with internal mixer and two-roll open mill. Mechanical properties and low-temperature performance (TR10) of the NBR/HNBR blends after aging under different conditions were investigated. Furthermore, equilibrium swelling test and moving die rheometer (MDR) test were used to systematically investigate the effects of HNBR dosage on the crosslink densities and curing behaviors. Vulcanization torque and crosslink densities decreased with an increase in HNBR content. The crosslink density of pure HNBR is higher than that of pure NBR, which is related to the macromolecular structures of the rubber. Compression sets of the NBR/HNBR vulcanizates were correlated with HNBR dosage indicating a linear relationship. Low-temperature performance of the NBR/HNBR blends was improved after being aged in the synthetic hydrocarbon hydraulic oils (SH-1 and SH-2). This work shows that the low-temperature performance and oil resistance could be better balanced by blending NBR with HNBR, while the mechanical properties maintain relatively high level.     

Polymerization of ethyl 2-cyanoacrylate in the presence of poly(butadiene-co-acrylonitrile)

Radical graft copolymers of ethyl 2-cyanoacrylate on to poly(butadiene-co-acrylonitrile), were prepared and characterized by infrared spectroscopy. Simultaneous homopolymerization of ethyl 2-cyanoacrylate also occurred. The polymerization of ethyl 2-cyanoacrylate is significantly affected by the presence of the pre-formed dissolved elastomer, the overall activation energies in the presence and absence of elastomer being 80.8 ± 0.4 kJ mol^?1 and 77.0 ± 0.4 kJ mol^?1, respectively. In each case the reaction was first-order with respect to the monomer.     

Thermal-oxidative aging behavior of graphene and graphene oxide-filled nitrile butadiene rubber: A molecular simulation approach

Nitrile rubber (NBR) is commonly used as a stator rubber for screw pumps because of its excellent mechanical properties. However, under high-temperature conditions, using NBR for long-term operations is difficult, since it is highly susceptible to a thermal-oxidative aging phenomenon that leads to its failure. In this study, the thermal-oxidative aging behavior of graphene and graphene oxide (GO) in an NBR composite system was investigated using simulated molecular dynamics at 298 K and 348 K. The results showed that Young's moduli of graphene/NBR and GO/NBR composite systems were enhanced by about 33% and 44%, respectively, when the temperature was increased. That is, adding graphene and GO improved the resistance of NBR composites to elastic, bulk, and shear deformation, playing an important role in slowing down the thermal and oxygen aging of rubber. Furthermore, the binding energy, mean square displacement, and free volume fraction of the NBR composite systems were analyzed. The abundant oxygen-containing functional groups in GO increased the intermolecular interaction force between GO and NBR and effectively inhibited the migration of antioxidants 4020. Therefore, GO retards the thermal and oxygen aging of NBR composite systems more effectively.     

溶剂对丁腈橡胶溶解、尺寸、结构和催化加氢的影响研究

丁腈橡胶（NBR）是由丁二烯和丙烯腈共聚而制得的一种重要的合成橡胶,而由NBR选择性加氢制得的氢化丁腈橡胶（HNBR）,不仅保持了NBR原有的耐油和耐磨性,其耐侯性、耐臭氧性等均得到极大改善,被广泛用于武器部件、航天用密封件等领域,是不饱和聚合物化学改性领域的一个重要研究课题。本文采用纳米粒度仪、乌氏黏度计、傅里叶变换红外等表征手段,结合密度泛函理论计算（DFT）,系统研究了溶剂性质对NBR在溶剂中的溶解行为、尺寸分布、分子结构及催化加氢性能等的影响。实验结果表明强亲电子溶剂不能溶解NBR,给电子溶剂及部分弱亲电子溶剂能较好地溶解NBR,特别是在酮类溶剂中,NBR粒径小且分布集中。DFT结果表明相比于气相氛围,在所有溶剂氛围中NBR链段里双键的键长均有所增长,且随着溶剂的极性增加而呈增长的趋势,NBR的偶极矩也随着溶剂极性增加而增加。特别是在酮类溶剂中,受溶剂效应的影响NBR分子的HOMO轨道由分子边缘向分子内部移动,表明对链段内部CC双键可能产生积极的影响。加氢结果表明在给电子溶剂中的加氢效果均优于弱亲电子溶剂,但无论选择何种溶剂,对NBR中CC双键的加氢选择性均为100%。该研究为NBR非均相溶液加氢体系中溶剂的筛选提供了理论依据。     

DMA analysis of the damping of ethylene–vinyl acetate/acrylonitrile butadiene rubber blends

The mechanical and damping properties of blends of ethylene–vinyl acetate rubber (VA content > 40% wt) (EVM)/acrylonitrile butadiene rubber (NBR), with 1.4 phr BIPB [bis (tert‐butyl peroxy isopropyl) benzene] as curing agent, were investigated by DMA and DSC. The effect of chlorinated polyvinyl chloride (CPVC), silica, carbon black, and phenolic resin (PF) as a substitute curing agent, on the damping and mechanical properties of EVM/NBR blends were studied. The results showed that 10 phr CPVC did not contribute to the damping of EVM700/NBR blends; Silica could dramatically improve the damping of EVM700/NBR blends because of the formation of bound rubber between EVM700/NBR and silica, which appeared as a shoulder tan δ peak between 20 and 70°C proved by DMA and DSC. This shoulder tan δ peak increased as the increase of the content of EVM in EVM/NBR blends. The tensile strength, modulus at 100% and tear strength of the blend with SiO₂ increased while the elongation at break and hardness decreased comparing with the blend with CB. PF, partly replacing BIPB as the curing agent, could significantly improve the damping of EVM700/NBR to have an effective damping temperature range of over 100°C and reasonable mechanical properties. Among EVM600, EVM700, and EVM800/NBR/silica blend system, EVM800/NBR/silica blend had the best damping properties. The EVM700/NBR = 80/10 blend had a better damping property than EVM700/NBR = 70/20. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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.     

Improvement of properties of silica‐filled styrene–butadiene rubber compounds using acrylonitrile–butadiene rubber

Since silica has strong filler–filler interactions and adsorbs polar materials, a silica‐filled rubber compound has a poor dispersion of the filler and poor cure characteristics. Improvement of the properties of silica‐filled styrene–butadiene rubber (SBR) compounds was studied using acrylonitrile–butadiene rubber (NBR). Viscosities and bound rubber contents of the compounds became lower by adding NBR to the compound. Cure characteristics of the compounds were improved by adding NBR. Physical properties such as modulus, tensile strength, heat buildup, abrasion, and crack resistance were also improved by adding NBR. Both wet traction and rolling resistance of the vulcanizates containing NBR were better than were those of the vulcanizate without NBR. The NBR effects in the silica‐filled SBR compounds were compared with the carbon black‐filled compounds. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1127–1133, 2001     

Peel stress relaxation of aluminium-aluminium joints bonded by chlorobutyl rubber-carboxylated nitrile rubber blend

The authors have introduced the concept of peel stress relaxation during 180° peel testing of an aluminium-adhesive-aluminium joint in order to explore the correlation, if any, between relaxation phenomenon and performance of the adhesive joint. The adhesive is based on a self-vulcanizable rubber blend of chlorobutyl rubber and carboxylated nitrile rubber. Peel stress relaxation depends on moulding time, silica filler loading, test temperature and peel rate. Peel stress relaxation mechanism varies depending on whether the adhesive joint failure is cohesive or interfacial.     

高性能橡胶/黏土纳米复合材料的制备与结构

研究了硬脂酸(SA)处理有机黏土(OC)制备橡胶/黏土纳米复合材料的结构与性能,并与未处理的OC制备的纳米复合材料进行了对比。结果表明,SA上的—COOH与OC片层表面的—OH发生了酯化反应,促使SA插层进入OC层间,使层间距扩大。采用SA处理OC制备出分散相态细致均匀、力学性能优异的丁腈橡胶/黏土(NBR/SA-OC)纳米复合材料;当OC与SA的质量比为10∶6时,纳米复合材料的性能最优。用带有极性和反应官能团的橡胶制备橡胶/黏土纳米复合材料,OC的分散性更好,与未处理的OC制备的纳米复合材料相比力学性能更优。     

用分子动力学模拟研究丁二烯微观结构对丁腈橡胶物理机械性能的影响

采用分子动力学模拟的方法对基于3种不同丁二烯键合结构建立的丁腈橡胶模型(A、B、C模型)进行了模拟计算,以考察丁二烯微观结构对丁腈橡胶物理机械性能的影响.采用恒定应变法计算模型的物理机械性能,然后将模型与铁原子层结合建立摩擦副模型,利用剪切模拟分析丁腈橡胶摩擦过程的磨损机理.结果表明,与A模型和C模型相比,B模型分子链...     

Influence of curing agent and compatibilizer on the physicomechanical properties of polypropylene/nitrile butadiene rubber blends investigated by positron annihilation lifetime technique

A series of thermoplastic vulcanizates of polypropylene (PP)/nitrile butadiene rubber (NBR) (50/50) have been prepared by melt‐mixing method, using phenolic resin/SnCl₂ as the curing system and maleic anhydride‐functionalized PP (PP‐g‐MA) and carboxylated NBR (NBRE‐RCOOH) as the compatibilizing system. Triethylenetetramine was also employed to promote the reaction between the functionalized polymers. The effects of curing agent and compatibilizer on the mechanical and morphological properties have been studied. A novel technique based on positron annihilation lifetime spectroscopy has been used to measure the free volume parameters of these systems. The positron results showed minimum free volume size and free volume fraction at 5.0% of the curing agent suggesting some crosslinking in the rubber phase. The reduction in free volume holes at 2.5% of the compatibilizer is interpreted as improvement in the interfacial adhesion between the components of the blend. The observed variation of free volume fraction is opposite to the tensile strength and exhibits the correlation that, lesser the free volume more is the tensile strength at 2.5% of the compatibilizer in the blend. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4672–4681, 2006     

Improvement of the homogeneity of SBR/NBR blends using polyglycidylmethacrylate‐g‐butadiene rubber

Polyglycidylmethacrylate grafted butadiene rubber (PGMA‐g‐BR) was synthesized by a graft solution copolymerization technique. The PGMA content was determined through titration against HBr. The PGMA‐g‐BR was blended with styrene butadiene rubber/butadiene acrylonitrile rubber (SBR/NBR) blends with different blend ratios. The SBR/NBR (50/50) blend was selected to examine the compatibility of such blends. Compatibility was examined using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and viscosity measurements. The scanning electron micrographs illustrate the change of morphology of the SBR/NBR rubber blend as a result of the incorporation of PGMA‐g‐BR onto that blend. The T_gs of SBR and NBR in the blend get closer upon incorporation of PGMA‐g‐BR 10 phr, which indicates improvement in blend homogeneity. The intrinsic viscosity (η) versus blend ratio graph shows a straight‐line relationship, indicating some degree of compatibility. Thermal stability of the compatibilized and uncompatibilized rubber blend vulcanizates was investigated by determination of the physicomechanical properties before and after accelerated thermal aging. Of all the vulcanizates with different blend ratios under investigation, the SBR/NBR (25/75) compatibilized blend possessed the best thermal stability. However, the SBR/NBR (75/25) compatibilized blend possessed the best swelling performance in brake fluid. The effect of various combinations of inorganic fillers on the physicomechanical properties of that blend, before and after accelerated thermal aging, was studied in the presence and absence of PGMA‐g‐BR. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1559–1567, 2006     

生物质硅炭增强改性氢化丁腈橡胶的性能及老化规律

以生物质硅炭(Si/CB)取代部分N550炭黑为补强剂、HNBR为基体制备了生物质硅炭改性的HNBR复合材料.研究了硅炭对HNBR的补强行为,高温真空介质中橡胶的热老化行为及主链老化结构的演变.与传统炭黑的增强效果相比,生物质硅炭增强的HNBR表现出更好的韧性、撕裂强度、较低的永久变形及高温力学性能.160℃下老化20...