环氧化天然橡胶与白炭黑及Si 69之间的反应及其对白炭黑填充溶聚丁苯橡胶性能的影响

研究了环氧化天然橡胶(ENR)与白炭黑及改性剂Si 69之间的反应及其对白炭黑/溶聚丁苯橡胶复合材料中白炭黑的分散状况以及复合材料力学性能的影响。结果表明,ENR中的环氧基团开环与白炭黑发生反应,但不能开环与Si 69发生反应。由于ENR与白炭黑的反应速率较慢,导致ENR改性白炭黑在溶聚丁苯橡胶混炼胶与硫化胶中的分散状况有所不同。但是将ENR和Si 69同时加入到白炭黑/溶聚丁苯橡胶复合材料中后,与只用Si 69改性白炭黑填充的溶聚丁苯橡胶相比,硫化胶的拉伸强度基本不变,定伸应力、硬度和撕裂强度增大,扯断伸长率和拉伸永久变形减小,这是因为加入ENR和Si 69后即存在白炭黑与ENR及白炭黑与Si 69两种反应,并且ENR中的环氧基团可以活化其相邻的双键,加速硫化,从而导致硫化胶交联密度增大的缘故。     

天然虾青素改性白炭黑/天然橡胶复合材料的制备与性能

采用天然虾青素对白炭黑表面进行物理改性，并与天然橡胶（NR）制备成复合材料。利用RPA、DMA、SEM等测试手段对天然虾青素改性白炭黑/天然橡胶复合材料的结构与性能进行表征。结果表明，在硫化特性方面，与未采用天然虾青素改性白炭黑相比，采用天然虾青素改性白炭黑所得胶料的焦烧时间和工艺正硫化时间均缩短，促进了橡胶的硫化过程；在物理力学性能方面，所得硫化胶的拉伸强度基本不变，回弹性和耐磨性明显增加，压缩生热降低；在动态黏弹性方面，所得硫化胶的Payne效应明显降低，填料的分散性在一定程度上得到改善；在动态力学性能方面，所得硫化胶的滚动阻力降低，玻璃化转变温度提高。特别地，在耐老化方面，天然虾青素改性白炭黑/天然橡胶复合材料的耐热空气老化性能明显提高。     

Cure and mechanical properties of filled SMR L/ENR 25 and SMR L/SBR blends

The effect of blend ratio of natural rubber/epoxidized natural rubber (SMR L/ENR 25) and natural rubber/styrene‐butadiene rubber (SMR L/SBR) blends on scorch time (t₂), cure time (t₉₀), resilience, hardness, and fatigue properties were studied in the presence of carbon black and silica. An accelerated sulfur vulcanization system was used throughout the investigation. The scorch and cure times of the rubber compound were assessed by using a Moving‐Die Rheometer (MDR 2000). Resilience, hardness, and fatigue life were determined by using a Wallace Dunlop Tripsometer, a Wallace Dead Load Hardness Tester, and a Fatigue to Failure Tester, respectively. The results indicate that t₂ and t₉₀ decrease with increasing ENR 25 composition in the SMR L/ENR 25 blend whereas both values increase with increasing SBR content in the SMR L/SBR blend. This observation is attributed to faster cure in ENR 25 and higher saturation in SBR. Resilience decreases with increase in % ENR and % SBR but hardness shows the reverse behavior in their respective blends. The fatigue life increases with % ENR, but it passes through a maximum with % SBR in the respective blends. In all cases, aging lowers the fatigue life, a phenomenon that is caused by the breakdown of crosslinks in the vulcanizate. Differences in all the observed values between carbon black‐filled and silica‐filled blends are associated with the varying degrees of interaction and dispersion of the two fillers in the rubber blend matrix. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 47–52, 2001     

ENR改性陶土和填充NR硫化胶结构与性能的研究

采用环氧化天然橡胶（ENR25和ENR45）改性陶土,通过对混炼胶结合胶质量分数、硫化胶表观交联密度、补强性能和力学性能的测定,研究了ENR与陶土的相互作用,ENR的环氧化程度及ENR的用量对陶土和填充NR硫化胶结构与性能的影响。结果表明,ENR可提高陶土与NR间界面的作用强度,提高混炼胶的结合胶质量分数,增大硫化胶的表观交联密度,改善硫化胶的网络结构,提高陶土填充NR硫化胶的力学性能,其中ENR25对陶土的改性效果优于ENR45。     

Moisture cure and in-situ silica reinforcement of epoxidized natural rubber

Epoxidized natural rubber (ENR) was first precured with 3-aminopropyltriethoxysilane (APS) by the normal compression molding technique. The resultant sheet was further subjected to moisture cure, via hydrolysis and condensation reactions, by soaking it in water. The moisture-cured sample, when prepared under appropriate reaction conditions, demonstrated partial strain-induced crystallization behavior and moderate tensile strength, as opposed to typical peroxide-cured and sulfur-cured vulcanizates. The suitability of the ENR–APS precured sample for in-situ silica reinforcement by the sol–gel process, using tetraethyl orthosilicate (TEOS) as the silica precursor, was also demonstrated. Silica content as high as 36% by weight could be incorporated into the rubber, and TEOS-to-silica conversion of over 60% was observed. Comparative analysis with a typical peroxide-cured sample that was subjected to the same sol–gel process indicates that the silica in the final ENR–APS sol–gel vulcanizate is chemically bound to the rubber network.     

炭黑并用对NR／ENR共混胶力学性能及减震性能的影响

对比N660研究了N330／N660、N660／N990炭黑填充体系对天然橡胶（NR）／环氧化天然橡胶（ENR）共混胶力学性能、压缩疲劳生热性能及减震性能的影响,并采用橡胶加工分析仪（RPA）对其加工性能进行了分析。结果表明：N660／N330和N660／N990两种填充体系硫化胶的力学性能,基本上是单用一种炭黑所得硫化胶力学性能的加权平均;不同粒径炭黑并用均能使共混胶的贮能模量E′下降,并且有利于拓宽NR／ENR减震材料的减震范围;不同粒径炭黑并用有利于改善NR／ENR共混胶料的加工性能。     

Influences of purification and surface treatment of sugarcane bagasse ash on mechanical properties of natural rubber composites

Attempts to use bagasse ash (BA) as a filler in natural rubber (NR) have been made. Acidolysis/alkaline extraction method was used to purify BA. The purified BA (PBA) was subsequently characterized by various techniques such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and so forth. After the purification, PBA had a lower particle size and a higher specific surface area. XRD results showed that silica was the main composition of PBA while FTIR results revealed the existence of hydroxyl groups on the PBA surface. The reinforcement magnitude of PBA in NR was subsequently evaluated both without and with the addition of surface modifying agents, namely, bis-3-triethoxysilylpropyl tetrasulfide (TESPT) and epoxidized natural rubber (ENR). Due to its large particle size, PBA acted as a semi-reinforcing filler for NR, that is, the small increases of hardness, modulus and tensile strength were observed in the presence of PBA. As TESPT and ENR could improve the extent of rubber-filler interaction, mechanical properties of the NR vulcanizates filled with PBA-TESPT and PBA-ENR were slightly higher than those of the PBA-filled NR vulcanizate. For instance, tensile strength exhibited approximately 22% increase after the surface treatment. In this study, both PBA-TESPT and PBA-ENR showed comparable degree of reinforcement.     

Reinforcing effect of silica on the properties of styrene butadiene rubber–reclaim rubber blend system

Incorporation of silica into styrene butadiene rubber (SBR)–reclaim rubber (RR) blend system was carried out by sol–gel technique and conventional method. A well known silica coupling agent bis(3‐triethoxysilyl propyl) tetrasulfide was found to affect the curing characteristics and mechanical properties of SBR/RR vulcanizate. Here, the effect of RR on silica reinforcement was studied for different SBR/RR blend system. Silica incorporation by conventional mechanical mixing in absence of TESPT showed a much higher tensile properties than that of silica incorporated by the in situ sol–gel reaction of tetraethoxy silane both in presence and absence of TESPT. Studies of equilibrium swelling in a hydrocarbon solvent were also carried out. ATR study indicates that RR forms bond with silica particles due to the presence of active functional site on RR. The amount of silica incorporated by sol–gel reaction was determined through thermogravimetric analysis (TGA). Scanning electron microscopy (SEM) studies further indicate the coherency and homogeneity in the silica filled SBR/RR vulcanizate. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 957–968, 2006     

Compatibility of epoxidized natural rubber with thermoplastic and thermosetting resins

The compatibility behavior of epoxidized natural rubber (ENR) at two different degrees of epoxidation with hydroxyl-containing polymeric resins was investigated. These included Novolac and Resole resins, the cured epoxy of bisphenol A (CER), and phenoxy. For each system, compositions covering the complete range were studied using the dynamic mechanical (DMA), DSC and phase-contrast microscopy techniques. ENR/Novolac blends were compatible, ENR/Resole, and ENR/phenoxy semicompatible, and ENR/CER incompatible. The results were interpreted in terms of the acid character of the aromatic or aliphatic hydroxyl contained in the resin and a predictive compatibility scheme based on copolymer-copolymer miscibility theory was tested.     

Role of geopolymer as a cure activator in sulfur vulcanization of epoxidized natural rubber

Geopolymer (GP) was synthesized and used as activators in sulfur vulcanization of epoxidized natural rubber (ENR). Influences of GP on cure characteristics, crosslink density, mechanical, thermal, and morphological properties were investigated and compared to the conventional rubber formulation with ZnO activator. The ZnO is a hazardous chemical for the environment and has proclaimed that its application in rubber technology should be reduced and controlled. It was found that the GP-activated ENR compounds showed significantly higher vulcanization rate than cases with the conventional ZnO compound. This was indicated by the GP activated compounds having shorter scorch time, cure times, and lower activation energy but higher cure rate index (CRI). Also, the GP activated ENR compounded with stearic acid exhibited the highest conversion. This matches well the highest torque difference and crosslink density, observed by temperature scanning stress relaxation (TSSR) and swelling measurements. Furthermore, the GP-activated vulcanizate had better thermal stability than the ZnO-activated ENR material. In addition, the GP-activated ENR vulcanizate with stearic acid exhibited high 100% moduli, tensile strength, and hardness. This proves that GP has a high potential for use as activators in sulfur vulcanization of rubber compounds, as an alternative to the conventional ZnO. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48624.     

碱法制备蔗渣纳米纤维素/丁苯橡胶复合材料性能

针对目前硫酸法制备纳米纤维素高污染、高危险、高处理成本的缺点,采用环境友好、低能耗、低成本的碱法从蔗渣中制备纳米纤维素（2-BNC）,补强丁苯橡胶（SBR）,并与硫酸法制备的纳米纤维素（S-BNC）以及白炭黑（silica）补强SBR的性能进行对比,探究2-BNC的加入对复合材料性能的影响。结果表明,2-BNC在基体中的分散性优于silica,与SBR基体有良好的界面结合,在同等填料份数下,SBR/2-BNC硫化胶的储能模量高于SBR/silica硫化胶,损耗因子下降,耐磨耗性能更加突出,且力学性能更佳;2-BNC和S-BNC对SBR的整体补强效果相当。     

Studies on novel dual filler based epoxidized natural rubber nanocomposite

Carbon black (N‐330), organically modified nanoclay (NC) based ternary, particulate nanocomposites comprising of epoxidized natural rubber matrix having 25 mol% of epoxy group (ENR‐25) were prepared in an open two‐roll mill. Investigations of cure characteristics, dynamic mechanical, tensile, thermal, and morphological characteristics were conducted using Rheometric analysis, Dynamic Mechanical Analysis (DMA), mechanical property evaluation, Thermo‐gravimetric analysis (TGA), High Resolution Transmission Electron Microscopy (HR‐TEM), respectively, to derive the interrelation among the developed nanostructures inside the composite, crosslinking density, performance properties obtained there from. A satisfactory level of correlation was obtained among various results, which indicated the formation of “nanounit” comprising of N‐330 and NC inside ENR‐25 matrix. To optimize the nanostructures, ENR based compounds containing various combinations of NC and N‐330 was prepared. Thorough and systematic structure‐property analyses were performed on those composites. Optimum stoichiometric combination of N‐330 and NC inside the ENR‐25 matrix was derived (ratio of N‐330 and nanoclay in wt% = 20:15), which showed synergistic effect of one filler upon another that was ultimately reflected in their dynamic mechanical and tensile properties. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

环氧化天然橡胶复合材料性能研究

采用新方法制备环氧化天然橡胶(ENR)/白炭黑和天然橡胶(NR)/ENR/白炭黑复合材料,并对其性能进行研究。结果表明:ENR/白炭黑复合材料的热稳定性优于ENR;在NR/ENR并用胶中加入白炭黑和硅烷偶联剂KH-550,NR/ENR/白炭黑复合材料0℃时的损耗因子(tanδ)增大,65℃时的tanδ值减小,复合材料的抗湿滑性能提高,滚动阻力减小。     

Effects of coagulation processes on properties of epoxidized natural rubber

The epoxidized natural rubber (ENR) with epoxy group contents of 48.4% were coagulated with ethanol and steam and the structures, processing performances, antioxidative behaviors, cure characteristics, and dynamic mechanical properties were analyzed using infrared spectroscopy, rubber processing analyzer, thermogravimetric analyzer, rheometer, and dynamic thermomechanical analyzer, respectively. The results indicate that the ENR coagulated with ethanol (ENR‐e) exhibits a compact structure and the contents of residual low‐molecular‐weight matters are higher than those of unconsolidated ENR coagulated with steam (ENR‐s). Therefore, the processing performance and antioxidative behavior as well as the curing characteristics of ENR‐e compound are poorer than those of ENR‐s. Although the mechanical properties and wet skid resistance of ENR‐s vulcanizate are poorer than those of ENR‐e, the heat build‐up or rolling resistance of ENR‐s is better than that of ENR‐e. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Mechanical and dynamic mechanical properties of natural rubber blended with waste rubber powder modified by both microwave and sol–gel method

Waste rubber powder (WRP) was modified by microwave, sol–gel method, and both microwave and sol–gel method, respectively. The mechanical and dynamic mechanical properties of natural rubber (NR)/modified WRP composite were investigated. The influence of bis‐(3‐(triethoxysilyl)‐propyl)‐tetrasulfide (TESPT) content on curing characteristics and mechanical properties of vulcanizate was also studied. The results showed that NR/WRP modified by both microwave and sol–gel method composite owned the best mechanical properties. Rubber processing analyzer was used to characterize the interaction between silica and rubber chains and the dispersion of silica. With increase of TESPT content, the Payne effect decreased. Scanning electron microscopy indicated the coherency and homogeneity of in situ generated silica filled vulcanizate. Dynamic mechanical analyzer showed that NR/WRP modified by both microwave and sol–gel method composite with 5 phr TESPT exhibited the lower tan δ at temperature range of 50–80°C, compared with composite without TESPT and the higher tan δ at temperature of 0°C, compared with the conventional modification of WRP. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

原位生成甲基丙烯酸锌对天然胶/气相法白炭黑纳米复合材料力学性能及加工性能的作用

研究了气相法白炭黑及甲基丙烯酸锌（ZDMA）对天然胶的力学性能、加工性能的影响.ZDMA采用原位生成的方法制备.力学性能的结果表明：ZDMA和气相法白炭黑对NR有协同补强的效应.橡胶加工性能分析（RPA）表明：ZDMA的加入,不仅能使天然胶/气相法白炭黑体系的加工性能得到很好的改善,而且能降低60 ℃时硫化胶的损耗因子.     

Self‐crosslinkable epoxidized natural rubber–silica hybrids

Epoxidized natural rubber (ENR)–silica hybrids without any other additives were prepared by an open‐mill mixing method at room temperature. The curing characteristics, crosslinking density, mechanical properties, and dynamical mechanical properties were investigated. The results indicate that the ENR–silica hybrid materials could be cured with silica as a crosslinking and reinforcing agent. Attenuated total reflection–Fourier transform infrared spectroscopy and solid‐state ¹³C‐NMR spectroscopy exposed the characteristics of the interfacial interaction in the hybrids and confirmed the existence of chemical bonds and hydrogen bonds between the epoxy group and Si? OH. Scanning electron microscopy illustrated a good dispersion of silica in the ENR matrix. Meanwhile, the modulus at 100% elongation of the hybrid reached 9.64 MPa when 100‐phr silica was loaded; a similar trend was observed for the hardness. Finally, our findings might extend the concept of rubber curing and open a new space for making an environmentally friendly rubber composite. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44605.     

EPDM/ENR共混胶力学性能的研究

探讨了三元乙丙橡胶(EPDM)和环氧化天然橡胶(ENR)的共混比、加料顺序、硫化体系对EPDM/ENR共混物的硫化特性、力学性能和耐热空气老化性能的影响。结果表明,共混比不同,共混胶的性能均有差异,且共混物的力学性能低于单组分的线性加和值,但综合比较而言,当EPDM/ENR=40/60时共混胶的力学性能较好;在所研究的四种加料顺序中,以配合剂先与EPDM制成母炼胶后再与ENR共混的这一种加料顺序下所得的共混物硫化胶的力学性能最好;采用半有效硫化体系所制得的共混物硫化胶的力学性能较好。     

白炭黑在环氧化天然橡胶中的应用

摘要：研究在不使用任何偶联剂的条件下,白炭黑在环氧化天然橡胶（ENR）中的应用。白炭黑在天然橡胶（NR）中会发生明显的团聚,而在ENR中的团聚情况可得到明显改善,且ENR的环氧化程度越高,白炭黑的分散性越好。ENR白炭黑胶料表现出良好的抗湿滑性能和较低的滚动阻力,白炭黑用量大T20份时,ENR/白炭黑胶料的压缩生热明显低于NR／炭黑胶料。     

On the potential of organoclay with respect to conventional fillers (carbon black,silica) for epoxidized natural rubber compatibilized natural rubber vulcanizates

Onium modified montmorillonite (organoclay) was compounded with natural rubber (NR) in an internal mixer and cured by using a conventional sulfuric system. Epoxidized natural rubber with 50 mol % epoxidation (ENR 50) in 10 parts per hundred rubber (phr) was used as a compatibilizer in this study. For comparison purposes, two commercial fillers: carbon black (grade N330) and silica (grade vulcasil‐S) were used. Cure characteristics were carried out on a Monsanto MDR2000 Rheometer. Organoclay filled vulcanizate showed the lowest values of torque maximum, torque minimum, scorch, and cure times. The kinetics of cure reaction showed organoclay could behave as a cocuring agent. The mechanical testing of the vulcanizates involved the determination of tensile and tear properties. The improvement of tensile strength, elongation at break, and tear properties in organoclay filled vulcanizate were significantly higher compared to silica and carbon black filled vulcanizates. In terms of reinforcing efficiency (RE), organoclay exhibited the highest stiffness followed by silica and carbon black filled vulcanizates. Scanning electron microscopy revealed that incorporation of various types of fillers has transformed the failure mechanism of the resulting NR vulcanizates compared to the gum vulcanizates. Dynamic mechanical thermal analysis (DMTA) revealed that the stiffness and molecular relaxation of NR vulcanizates are strongly affected by the filler–rubber interactions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2438–2445, 2004