丁腈橡胶增容丁苯橡胶/聚氯乙烯共混体系

采用一系列结合丙烯腈质量分数不同的丁腈橡胶(NBR)作为丁苯橡胶(SBR)／聚氯乙烯(PVC)不相容共混物的增容剂,研究了SBR／PVC／NBR硫化胶的力学性能,并用扫描电子显微镜、傅里叶变换红外光谱仪和动态黏弹仪研究了该硫化胶的形态结构与相容性。结果表明,结合丙烯腈质量分数为20％～26％的NBR是SBR／PVC的优良增容剂,可提高共混物的力学性能,使SBR相和PVC相达到微细均匀化分散,并在两相之间形成了界面层,使得增容效果达到最佳。     

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.     

丙烯酸酯橡胶与丁腈橡胶并用研究

对丙烯酸酯橡胶（ACM）与丁腈橡胶（NBR）并用胶的物理机构性能及耐热耐油性能进行了测试考察。实验结果表明,m(ACM):m(NBR)≥70:30的并用胶,综合性能比丁腈橡胶及丙烯酸酯橡胶好、成本低,可代替丙烯酸酯橡胶用作耐热耐油密封件胶料。     

Effect of different nanoparticles on thermal,mechanical and dynamic mechanical properties of hydrogenated nitrile butadiene rubber nanocomposites

Organically modified and unmodified montmorillonite clays (Cloisite NA, Cloisite 30B and Cloisite 15A), sepiolite (Pangel B20) and nanosilica (Aerosil 300) were incorporated into hydrogenated nitrile rubber (HNBR) matrix by solution process in order to study the effect of these nanofillers on thermal, mechanical and dynamic mechanical properties of HNBR. It was found that on addition of only 4 phr of nanofiller to neat HNBR, the temperature at which maximum degradation took place (T_max) increased by 4 to 16°C, while the modulus at 100% elongation and the tensile strength were enhanced by almost 40–60% and 100–300% respectively, depending upon nature of the nanofiller. It was further observed that T_max was the highest in the case of nanosilica‐based nanocomposite with 4 phr of filler loading. The increment of storage modulus was highest for sepiolite‐HNBR and Cloisite 30B‐HNBR nanocomposites at 25°C, while the modulus at 100% elongation was found maximum for sepiolite‐HNBR nanocomposite at the same loading. A similar trend was observed in the case of another grade of HNBR having similar ACN content, but different diene level. The results were explained by x‐ray diffraction, transmission electron microscopy, and atomic force microscopy studies. The above results were further explained with the help of thermodynamics. Effect of different filler loadings (2, 4, 6, 8, and 16 phr) on the properties of HNBR nanocomposites was further investigated. Both thermal as well as mechanical properties were found to be highest at 8 phr of filler loading. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Assembly of layered double hydroxide on multi‐walled carbon nanotubes as reinforcing hybrid nanofiller in thermoplastic polyurethane/nitrile butadiene rubber blends

An efficient approach has been applied to assemble MgAl layered double hydroxide onto pristine carbon nanotubes using sodium dodecylsulfate. The assembling process and formation of such hybrid nanostructures were established using X‐ray diffraction, Fourier transform infrared spectroscopy, field emission scanning electron microscopy and high‐resolution transmission electron microscopy. Subsequently, the hybrid was used as nanofiller in the development of high‐performance thermoplastic polyurethane/acrylonitrile butadiene rubber (1:1 w/w) blend nanocomposites. Measurements of mechanical and dynamic mechanical properties show that tensile strength, elongation at break and storage modulus improve significantly by 171%, 1.8 times and 241% in a blend with 0.50 wt% loading of hybrid filler. Thermogravimetric analysis shows that the thermal stability of the blend with 0.50 wt% hybrid filler compared to neat material is maximally improved by 20 °C determined at 50% weight loss. Differential scanning calorimetry shows the maximum enhancement in melting temperature (7 °C) and crystallization temperature (31 °C) due to significant nucleation efficiency of the filler, homogeneous dispersion and strong interfacial interaction between polymer matrix and filler. © 2015 Society of Chemical Industry     

Synthesis and characterization of polyurethane/Mg‐Al layered double hydroxide nanocomposites

Layered double hydroxide (LDH) is a new type of nanofiller, which improves the physicochemical properties of the polymer matrix. In this study, 1, 3, 5, and 8 wt % of dodecyl sulfate‐intercalated LDH (DS‐LDH) has been used as nanofiller to prepare a series of thermoplastic polyurethane (PU) nanocomposites by solution intercalation method. PU/DS‐LDH composites so formed have been characterized by X‐ray diffraction and transmission electron microscopy analysis which show that the DS‐LDH layers are exfoliated at lower filler (1 and 3 wt %) loading followed by intercalation at higher filler (8 wt %) loading. Mechanical properties of the nanocomposite with 3 wt % of DS‐LDH content shows 67% improvement in tensile strength compared to pristine PU, which has been correlated in terms of fracture behavior of the nanocomposites using scanning electron microscope analysis. Thermogravimetric analysis shows that the thermal stability of the nanocomposite with 3 wt % DS‐LDH content is ≈ 29°C higher than neat PU. Limiting oxygen index of the nanocomposites is also improved from 19 to 23% in neat PU and PU/8 wt% DS‐LDH nanocomposites, respectively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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。     

Ionic elastomer blends of zinc salts of maleated natural rubber and carboxylated nitrile rubber: Effect of grafted maleic anhydride

Zinc neutralized maleated natural rubbers (Zn‐MNR) were prepared by solution grafting and neutralization with zinc acetate in one‐step. It was later used for blending with carboxylated nitrile rubber (XNBR) in the composition of 50/50 parts by weight. The effect of grafted anhydride content (1.2, 1.6, 2.0, and 2.5% wt of NR) on the tensile properties of ionic rubber blends (Zn‐MNR/XNBR) was investigated. The tensile strength of the ionic blends was found to be greater than those of pure rubbers. The modulus, tensile, and tear strength of the blends dramatically increased with increasing levels of grafted anhydride. The ionic rubber blends also possessed superior physical properties compared to those of the corresponding nonionic rubber blends (MNR/XNBR). Dynamic mechanical thermal analysis and scanning electron microscopic studies were performed to verify the process of mixing. Fourier transform infrared spectroscopic studies were carried out to characterize the nature of specific intermolecular interactions between Zn‐MNR and XNBR chain segments. The results indicated that the ion‐ion (Zn⁺ ‐COO^?) interactions between Zn‐MNR and XNBR are formed at the interface, which provides the mean of compatibilization in the ionic rubber blends. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

氯醚橡胶/丁腈橡胶共混物的结构与性能

研究了不同并用比的氯醚橡胶（ECO）／丁腈橡胶（NBR）共混物的相态结构,力学性能,耐老化性能和耐油性能,透射电镜照片显示：ECO／NBR为70／30（质量份,下同）时共混物呈双连续相：为60／40和40／60时ECO都为分散相,且两相界面清晰。加入NBR降低了ECO的拉伸强度和看断伸长率,以及耐热空气老化性能,随着NBR用量的提高,共混物硫化胶在油中的体积变化率增加,ECO／NBR为70／30时硫化胶在100℃热油中的性能保持率最高,而且体积变化率与ECO的相当。     

Morphology,mechanical and viscoelastic properties of nitrile rubber/epoxidized natural rubber blends

A new class of blend membranes from blends of nitrile rubber (NBR) and epoxidized natural rubber (ENR) has been prepared and their morphology, miscibility, mechanical, and viscoelastic properties have been studied. The ebonite method was used to study the blend morphology of the membranes. The morphology of the blends indicated a two‐phase structure in which the minor phase is dispersed as domains in the major continuous phase. The performance of NBR/ENR blend membranes has been studied from the mechanical measurements. The viscoelastic behavior of the blends has been analyzed from the dynamic mechanical data. An attempt was made to relate the viscoelastic behavior with the morphology of the blends. Various composite models have been used to predict the experimental viscoelastic data. The area under the linear loss modulus curve was larger than that obtained by theoretical group contribution analysis. The homogeneity of the system was further evaluated by Cole–Cole analysis. Finally, a master curve for the modulus of the blend was generated by applying the time–temperature superposition principle. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1561–1573, 2005     

Natural rubber/nitrile butadiene rubber/hindered phenol composites with high-damping properties

New natural rubber (NR)/nitrile butadiene rubber (NBR)/hindered phenol (AO-80) composites with high-damping properties were prepared in this study. The morphological, structural, and mechanical properties were characterized by atomic force microscopy (AFM), polarized Fourier transform infrared spectrometer (FTIR), dynamic mechanical thermal analyzer (DMTA), and a tensile tester. Each composite consisted of two phases: the NR phase and the NBR/AO-80 phase. There was partial compatibility between the NR phase and the NBR/AO-80 phase, and the NR/NBR/AO-80 (50/50/20) composite exhibited a co-continuous morphology. Strain-induced crystallization occurred in the NR phase at strains higher than 200%, and strain-induced orientation appeared in the NBR/AO-80 phase with the increase of strain from 100% to 500%. The composites had a special stress–strain behavior and mechanical properties because of the simultaneous strain-induced orientation and strain-induced crystallization. In the working temperature range of a seismic isolation bearing, the composites (especially the NR/NBR/AO-80 (50/50/20) composite) presented a high loss factor, high area of loss peak (TA), and high hysteresis energy. Therefore, the NR/NBR/AO-80 rubber composites are expected to have important application as a high-performance damping material for rubber bearing.     

丁腈橡胶/橡塑材料并用研究进展

综述了近年来国内外丁腈橡胶与天然橡胶、丁苯橡胶、卤化丁基橡胶、三元乙丙橡胶、聚丙烯、聚氯乙烯、乙烯-乙酸乙烯共聚物、聚酰胺及其他橡塑材料并用改性的研究进展.     

Noncovalent assembly of carbon nanofiber–layered double hydroxide as a reinforcing hybrid filler in thermoplastic polyurethane–nitrile butadiene rubber blends

A new synthetic route was applied to develop carbon nanofiber (CNF)–layered double hydroxide (LDH) hybrid through a noncovalent assembly using sodium dodecyl sulfate as bridging linker between magnesium–aluminum LDH and CNF and then characterized. Furthermore, this hybrid was used as nanofiller in thermoplastic polyurethane–acrylonitrile butadiene rubber (TN; 1:1 w/w) blend. Mechanical measurements showed that the 0.50 wt % hybrid loaded TN blend exhibited the maximum improvements in the elongation at break, tensile strength, and storage modulus of 1.51 times and 167 and 261% (25 °C), respectively. Differential scanning calorimetric analysis and thermogravimetric analysis showed maximum improvements in the melting temperature (5 °C), crystallization temperature (17 °C), and thermal stability (14 °C) in the 0.50 wt % surfactant modified carbon nanofiber–LDH loaded blend compared to the neat blend. Such enhancement in the properties of the TN nanocomposites could be attributed to the homogeneous dispersion, strong filler–blend interfacial interaction, and synergistic effect. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43470.     

Rubber/LDH nanocomposites by solution blending

The rubber nanocomposites containing ethylene vinyl acetate (EVA) having 60 wt % of vinyl acetate content and organomodified layered double hydroxide (DS‐LDH) as nanofiller have been prepared by solution intercalation method and characterized. The XRD and TEM analysis demonstrate the formation of completely exfoliated EVA/DS‐LDH nanocomposites for 1 wt % filler loading followed by partially exfoliated structure for 5–8 wt % of DS‐LDH content. EVA/DS‐LDH nanocomposites show improved mechanical properties such as tensile strength (TS) and elongation at break (EB) in comparison with neat EVA. The maximum value of TS (5.1 MPa) is noted for 3 wt % of DS‐LDH content with respect to TS value of pure EVA (2.6 MPa). The data from thermogravimetric analysis show the improvement in thermal stability of the nanocomposites by ≈15°C with respect to neat EVA. Limiting oxygen index measurements show that the nanocomposites act as good flame retardant materials. Swelling property analysis shows improved solvent resistance behavior of the nanocomposites (1, 3, and 5 wt % DS‐LDH content) compared with neat EVA‐60. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and characterization of exfoliated layered double hydroxide/silicone rubber nanocomposites

Silicone rubber (SR)/Mg–Al layered double hydroxide (LDH) nanocomposites were prepared by the solution intercalation of SR crosslinked by a platinum‐catalyzed hydrosilylation reaction into the galleries of dodecyl sulfate intercalated layered double hydroxide (DS–LDH). X‐ray diffraction and transmission electron microscopy analysis showed the formation of exfoliated structures of organomodified LDH layers in the SR matrix. The tensile strength and elongation at break of SR/DS–LDH (5 wt %) were maximally improved by 53 and 38%, respectively, in comparison with those of the neat polymer. Thermogravimetric analysis indicated that the thermal degradation temperature of the exfoliated SR/DS–LDH (1 wt %) nanocomposites at 50% weight loss was 20°C higher than that of pure SR. Differential scanning calorimetry analysis data confirmed that the melting temperature of the nanocomposites increased at lower filler loadings (1, 3, and 5 wt %), whereas it decreased at a higher filler loading (8 wt %). The relative improvements in the solvent‐uptake resistance behavior of the SR/DS–LDH nanocomposites were also observed. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

片层硅酸盐纳米复合聚氨酯橡胶的结构及性能

将聚四氢呋喃二醇和富羟基活性蒙脱土(HMMT)进行预混插层处理,然后与甲苯二异氰酸酯(TDI)进行反应,得到层状硅酸盐复合预聚体。随后预聚体与扩链剂(DMTDA)反应制备出聚氨酯橡胶/片层硅酸盐纳米复合材料。采用材料拉伸机、X射线衍射(XRD)、透射电镜 (TEM)、差示扫描量热仪 (DSC)和热失重分析仪 (TGA) 等检测设备对聚醚型聚氨酯脲的结构与性能进行分析。结果表明：当PMMT的质量百分含量在2％时,片层硅酸盐粒子在聚氨酯基体内分散较均匀,形成了以剥离型为主、插层型为辅的复合型结构,聚醚型聚氨酯脲复合材料的拉伸强度比纯PUU提高了21%,断裂伸长率提高了12%,PUU复合材料的玻璃化转变温度(Tg)提高了5.8℃,第一失重区分解温度和最高分解温度高出纯聚氨酯17.33 ℃和13.94 ℃。无机纳米片层硅酸盐粒子的存在,聚氨酯橡胶的强度、韧性和热稳定性均得到改善。     

Effect of bilayered stearate ion‐modified Mg?Al layered double hydroxide on the thermal and mechanical properties of silicone rubber nanocomposites

The homogeneous dispersion of nanofillers in polymer matrices to form polymer nanocomposites remains a challenge in the development of high‐performance polymer materials for various applications. In the work reported, a stearate ion‐modified Mg? Al layered double hydroxide (St‐LDH) as nanofiller was incorporated in a silicone rubber (SR) matrix by solution intercalation and subsequently characterized. X‐ray diffraction and transmission electron microscopy studies confirm the formation of a predominantly exfoliated dispersion of St‐LDH layers of 75–100 nm in width and about 1–2 nm in thickness in the SR. Thermogravimetric analysis shows that the thermal degradation temperature of the exfoliated SR/St‐LDH (1 wt%) nanocomposites is about 80 °C higher than that of pure SR. Differential scanning calorimetric studies indicate that the melting and crystallization temperatures are higher by 4 and 10 °C for 5 and 8 wt% St‐LDH‐loaded SR nanocomposites compared to neat SR. A significant improvement of 97% in tensile strength and 714% in storage modulus and a reduction of 82% in oxygen permeability have been achieved at 3 wt% St‐LDH loading in SR. Copyright © 2011 Society of Chemical Industry     

Exploring the role of stearic acid in modified zinc aluminum layered double hydroxides and their acrylonitrile butadiene rubber nanocomposites

The proposed study attempted to explore the role of stearic acid modification on the properties of zinc‐aluminum based layered double hydroxides (LDH) and their composites with acrylonitrile butadiene rubber (NBR). Three distinctive LDH systems were adapted for such comparison; an unmodified LDH and two stearic acid modified LDH. The use of zinc oxide and stearic acid in the rubber formulation was avoided as the modified LDH would be able to deliver the necessary activators for the vulcanization process. Emphasis was predominantly given to reconnoiter the merits of stearic acid modification on the increase in interlayer distance of the LDH. X‐ray diffraction studies and transmission electron microscope morphological investigations of LDH powders indicated that modification with stearic acid increased the interlayer spacing which would favor the intercalation of NBR polymer chains into the layered space. However, stress–strain studies indicated better mechanical properties for composites with unmodified LDH. Composites with LDH showed higher crosslinking densities than conventionally sulfur cured control compounds using zinc oxide/stearic acid as activators. This was evident from equilibrium swelling method as well as statistical theory of rubber elasticity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41539.     

机械共混法制备丁腈橡胶/聚氯乙烯/有机蒙脱土纳米复合材料的结构及性能

用机械共混法将4种牌号的有机蒙脱土(OMMT)与丁腈橡胶(NBR)/聚氯乙烯(PVC)共混,制备了纳米复合材料,并对其微观结构、硫化特性、力学性能以及耐油性进行了考察.结果表明,该复合材料具有插层型结构;4种牌号的OMMT均能提高共混胶的硫化速率,且能提高纳米复合材料的力学性能,其中牌号为FMR 11的OMMT增强效果最好,当其用量为6份时,纳米复合材料的拉伸强度比纯胶提高了49.96%,撕裂强度提高了36.9%,扯断伸长率也有所提高;随着OMMT用量的增加,纳米复合材料的耐油性逐渐提高.     

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。