界面改性剂对天然橡胶/纳米粘土复合材料性能的影响

以4个不同厂家的界面改性剂改性纳米粘土,以乳液共混法制备天然橡胶(NR)/纳米粘土复合材料,研究界面改性剂对复合材料性能的影响。结果表明,不同厂家界面改性剂的理化性能及其改性的纳米粘土制得的复合材料性能差异明显,有的厂家界面改性剂改性的纳米粘土与NR的结合较好,有的厂家界面改性剂改性的纳米粘土制得的复合材料硫化效率较高。     

阴/阳离子表面活性剂复配改性粘土/橡胶纳米复合材料的结构与性能

采用阴离子表面改性剂十二烷基磺酸钠(SDS)与阳离子表面改性剂十八烷基三甲基溴化铵(STAB)复配改性粘土,制备有机粘土/橡胶纳米复合材料,考察其结构和性能。结果表明:当SDS/STAB质量比为2/4时,有机粘土/丁腈橡胶(NBR)纳米复合材料的综合物理性能最优,STAB的有机阳离子取代无机粘土层间可交换的阳离子,SDS通过碳-氢键与无机粘土层间非极性较强的质点发生范德华力及离子静电吸附作用,获得晶层间距更大的有机粘土;与非极性的丁苯橡胶和天然橡胶相比,极性的NBR使粘土的远程聚集趋势减小和界面吸附作用增强,相应复合材料的物理性能增幅更大。     

含有环氧化天然橡胶增容剂的天然橡胶/微晶纤维素复合材料

正橡胶和填料间界面相互作用是决定填充橡胶复合材料最终性能的关键因素。然而,橡胶-填料间相互作用的有效性在很大程度上取决于填料表面基团的性质。非极性NR基质和极性填料表面相互作用非常微弱。正因如此,一些研究人员报道了将环氧化NR(ENR)用作增容剂,增强天然橡胶和不同极性填料(例如与白炭黑、有机粘土和改性膨胀石墨)间相互作用的成功案例。ENR是NR的一种重要的极性衍生物,其结构中含有随机分布的环氧化基团。ENR-50具有很高的耐油性能,低透气性以及较高的阻尼性能。对于     

有机粘土／SBR纳米复合材料的结构与性能研究

采用十六烷基三甲基溴化铵（CTAB）和十八烷基三甲基溴化铵（STAB）分别对无机粘土进行有机改性,然后制备有机粘上／SBR纳米复合材料,研究不同季铵盐类改性剂对无机粘土的改性效果。结果表明：CTAB改性有机粘土与STAB改性有机粘土的片层间距分别从无机粘土的1．26nm增加到3．77nm和4．39nm;CTAB改性有机粘土的片层结构较稳定,而且在橡胶基体中的分散效果较好;所制备的有机粘土／SBR纳米复合材料的片层结构较多,力学性能较好。     

有机改性的粘土与丁苯橡胶纳米复合材料的制备方法

由北京化工大学申请的专利（专利号CN1900149,公开日期2007-01-24）“有机改性的粘土与丁苯橡胶纳米复合材料的制备方法”,涉及的有机改性粘土／SBR纳米复合材料的制备方法是：先将有机改性剂（烷基铵盐）水溶液与粘土水悬浮液混合[有机改性剂与粘土的质量比为（10-50）：100],然后与丁苯胶乳混合,再经过破乳絮凝、干燥脱水、混炼、硫化得到产品。     

无机粘土的烷基铵盐改性及NBRCNs的结构与性能研究

采用长链脂肪族季铵盐改性有机粘土的方法,研究了烷基铵盐改性剂的碳链长度及配比对无机粘土(MMT)改性效果的影响。结果表明,同一改性剂配比下,由不同碳链长度的烷基铵盐改性剂改性MMT制备的丁腈橡胶/粘土纳米复合材料(NBRCNs)的微观结构、力学性能和分散相态不同,碳链长度适中的十二烷基三甲基溴化铵(CTAB)改性效果较好,碳链长度较长或较短都不利于MMT的改性。对于碳链长度较短的二十二烷基三甲基溴化铵(DTAB),当DTAB用量增加,粘土片层间距增大,力学性能提高。对于碳链长度较长的十八烷基三甲基溴化铵(STAB),STAB用量降低有助于扩大粘土片层间距和提高力学性能。     

粘土橡胶纳米复合材料研究进展

简要概述了粘土的有机改性机理、橡胶/粘土纳米复合材料的制备方法、结构与表征和橡胶/粘土纳米复合材料的研究进展.     

含羧基有机蒙脱土/天然橡胶纳米复合材料的结构与性能

通过蒙脱土与酸化椰油酰胺基丙基甜菜碱(CAB)进行正离子交换,制备了含羧基的有机蒙脱土(OMMT),用OMMT与天然橡胶(NR)复合制得插层型纳米复合材料。对OMMT的结构进行了表征,研究了OMMT对NR/OMMT纳米复合材料结构与性能的影响。结果表明,酸化CAB溶液改性OMMT的层间距较蒙脱土改性者有较大幅度的增加;少量OMMT可改善NR的拉伸强度和扯断伸长率,同时维持较低的拉伸永久变形;OMMT对复合材料的硫化表现出促进作用,但其含量对复合材料的硫化特性影响不大。     

硅烷偶联剂复合改性蒙脱土制备NR/OMMT纳米复合材料

采用硅烷偶联剂和十六烷基三甲基溴化铵(CTAB)作为复合改性剂制备有机蒙脱土,使有机蒙脱土的结构发生了改变.其中采用硅烷偶联剂KH570与CTAB复合改性的效果较好,得到了插层效果较好的NR/OMMT纳米复合材料.     

塑料改性用有机膨润土制备技术及应用的研究

本文采用不同的有机改性剂制备出有机膨润土(OMMT),并用所制备的有机膨润土分别制备出PU/OMMT、PBT/OMMT、PA6/OMMT纳米复合材料.经对复合材料力学性能分析结果表明:用N-烷基氨基酸改性膨润土所制备PU/OMMT、PA6/OMMT纳米复合材料性能最佳;用十六烷基三甲基溴化铵改性膨润土所制备PBT/OMMT纳米复合材料性能最佳.     

有机蒙脱土对天然橡胶/丁苯橡胶的补强及增容作用

采用机械混炼法制备了天然橡胶(NR)/丁苯橡胶(SBR)/有机蒙脱土(OMMT)纳米复合材料,采用TEM和XRD对复合材料的亚微观结构进行了表征,并对复合材料的表观交联密度、静态力学性能、动态力学性能和硫化热效应进行了研究。结果表明,复合材料为剥离型纳米复合材料;OMMT能够明显提高纳米复合材料的交联密度和静态力学性能;OMMT导致NR/SBR共混胶动态损耗因子降低,并且能够促使NR和SBR玻璃化转变温度更为接近,起到了增容作用;OMMT实现了NR和SBR两相的同步硫化。     

橡塑合金改性沥青制备工艺关键参数研究

为了合理、有效地利用废旧橡胶粉和废旧塑料并改善两者与沥青的相容性,采用精密开炼机预先将两种废旧材料熔融共混,制备成橡塑（质量）比分别为5∶5（Ⅰ型）、6∶4（Ⅱ型）、和7∶3（Ⅲ型）3种橡塑合金改性剂。按照正交试验方案对伦特70^#基质沥青进行改性,制备橡塑合金改性沥青,以橡塑合金改性沥青的48 h离析软化点、25 ℃针入度、软化点和5 ℃延度为指标,筛选橡塑合金改性沥青的最佳复配方案,并通过灰色关联度分析法和极差分析法确定制备工艺最佳的关键参数。最后通过扫描电子显微镜、布氏旋转黏度试验、BBR试验和DSR试验对橡塑合金改性沥青的结构形态、流变性能、低温抗裂性能和抗疲劳性能进行了分析。结果表明：最佳复配方案为外掺20 %（相较于基质沥青质量）橡塑比为7∶3（Ⅲ型）的橡塑合金、2 %增溶剂（糠醛抽出油）和9 %稳定剂（硫磺）,制备的橡塑合金改性沥青储存稳定性和高温稳定性良好,推荐制备工艺的最佳关键参数为剪切温度180 ℃、剪切速率3 500 r/min、剪切时间1.5 h和发育时间0.5 h;橡塑合金改性剂与沥青的相容性好,制备的橡塑合金改性沥青具有较低的温度敏感性,较好的低温抗裂性和抗疲劳性能。     

Properties of organo‐clay/natural rubber nanocomposites: Effects of organophilic modifiers

The effect of various modifiers on the structure and properties of clay/natural rubber nanocomposites are investigated with the aim to evaluate the effect of size and structure of the modifier. Nanocomposites are prepared by melt intercalation method. Mechanical properties of the cured rubber containing nanoclay are compared with the reference compound without the filler. No improvement of mechanical properties is observed for small organic cations; however, stress and strain at break of clay/rubber nanocomposites increase with rising number of octyl chains in the interlayer spaces of organo‐clays. Concerning organo‐cations with the same number of carbon atoms, more effective are the modifiers with several shorter carbon chains compared to those with one long chain. The composites exhibit hybrid structure of nanocomposite and microcomposite as revealed by X‐ray powder diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The details of the structure are supported by DMTA and hysteresis measurements. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

The role of surfactant type and modifier concentration in tailoring the properties of chlorobutyl rubber/organo clay nanocomposites

Nanocomposites were prepared using montmorillonite with different organic modifiers (cloisite 10 A, cloisite 15 A, and cloisite 20 A) and the effect of intercalant structure on clay morphology and chlorobutyl vulcanization kinetics was investigated. Because of its lower rigid structure the aliphatic salt was easier to intercalate into the clay galleries giving rise to a higher interlayer distance and facilitating the rubber intercalation obtaining an exfoliated structure in the nanocomposite. The vulcanization process was sensibly accelerated by this organoclay and a higher crosslinking degree was observed in the nanocomposite which gave rise to materials with improved processing and physical characteristics. The present work focuses on characterising the surfaces of organically modified MMT clays and the relationship to the final properties of their nanocomposites. Concentrating on the surface modifiers, one has to take into account their interaction with the matrix polymer, the solubility of the organic molecule adding to the complexity due to its influence. We aim to show that understanding the influence of surface characteristics is the basis for selecting the ideal organoclay for the given matrix polymer. Depending on the nature of the surfactant used for the organic modification of clay and its modifier concentration the nanocomposites exhibit difference in the properties. The organoclays used in the present study were selected to explore the effects of the amine surfactant structure on the dispersion of clay particles in chlorobutyl rubber matrix. The structure of the organic amine compound used to form the organoclay is expected to have some effect on the morphology and properties of the nanocomposites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

新型有机改性剂对重质碳酸钙的表面改性效果及机理

采用新型改性剂和传统改性剂对两种重质碳酸钙进行干法表面有机改性,探究了改性剂种类和改性剂用量对样品吸油值、活化指数、油相分散稳定性和水接触角的影响,确定了改性剂的优化用量,采用傅里叶变换红外光谱仪（FT-IR）、热重分析（TG）探究重质碳酸钙改性机理。结果表明：改性剂JST-9001（聚氧乙烯醚型复合改性剂）、JST-9003（聚氧乙烯醚型复合改性剂）、硬脂酸和铝酸酯F-2的改性效果更好,尤其两种新型改性剂JST-9001和JST-9003在低改性剂用量下（质量分数为0.5%）可获得更加优异的表面改性效果;优化用量下JST-9001和JST-9003改性剂分子中的亲水基与重质碳酸钙表面的—OH发生键合作用,改性剂分子层包覆于重质碳酸钙颗粒表面。     

Use of acrylic based surfmers for the preparation of exfoliated polystyrene–clay nanocomposites

Two polymerizable cationic surfactants, (11-acryloyloxyundecyl)dimethyl(2-hydroxyethyl)ammonium bromide (hydroxyethyl surfmer) and (11-acryloyloxyundecyl)dimethylethylammonium bromide (ethyl surfmer), were used for the modification of montmorillonite (MMT) clay. The modification of MMT dispersions was carried out by ion exchange of the sodium ions in Na⁺-MMT by surfactants in aqueous media. Modified MMT clays were then dispersed in styrene and subsequently polymerized in bulk by a free-radical polymerization reaction to yield polystyrene–clay nanocomposites. An exfoliated structure was obtained using the ethyl surfmer-modified clay, whereas a mixed exfoliated/intercalated structure was obtained using the hydroxyethyl surfmer-modified clay. Nanocomposite structures were confirmed by small angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). The nanocomposites exhibited enhanced thermal stability and an increase in glass transition temperature, relative to neat polystyrene. The nanocomposites also exhibited enhanced mechanical properties, which were dependent on the clay loading. Intercalated polystyrene–clay nanocomposites were obtained using the non-polymerizable surfactant-modified clay (cetyltrimethylammonium bromide). Nanocomposites made from mixtures of surfmer-modified and CTAB-modified clays were also prepared, showing intermediate properties. However, when the nanocomposites were prepared in solution only intercalated morphologies were obtained. This was attributed to the competition between the solvent molecules and monomer in penetrating into clay galleries. These nanocomposites also exhibited enhanced thermal stability relative to the virgin polystyrene prepared by the same method. Similar temperatures of degradation (at 50% decomposition) were found for these nanocomposites relative to those prepared by bulk polymerization.     

Immobilization of TiO2 nanoparticles on montmorillonite clay and its effect on the morphology of natural rubber nanocomposites

Natural rubber/organoclay/titanium dioxide nanocomposites were obtained via mechanical blending using rubber latex, organically modified montmorillonite clay (cloisite 30B) and titanium dioxide (TiO₂). Glycerol was utilized as a dispersant for the inorganic components. Scanning electron microscopy analysis shows that TiO₂ nanoparticles were deposited on the clay surface and that the clay–TiO₂ combination was homogeneously dispersed on the natural rubber. The high aspect ratio and the polar character of the clay layers allowed interactions with individual nanoparticles of TiO₂. The X-ray diffraction patterns reveal an increment of the crystalline character of the NR/C30B/TiO₂ nanocomposites as a consequence of the nanoscale dispersion of the TiO₂ particles. Infrared Spectroscopy spectra indicate compatibility between natural rubber and glycerol due to the formation of hydrogen bonds. A mechanism in particle–natural rubber compatibility, in which glycerol is involved, is proposed. However, nanoscale dispersion was largely dependent on the clay–TiO₂ interactions. This work proposes an easy method to immobilize TiO₂ nanoparticles on clay layers, which allows their dispersion in polymers. Nanocomposites obtained by this method can be used for supports of photocatalyst molecules.     

“胶乳共混法”制备天然橡胶／二氧化硅纳米复合材料及其性能

采用γ-甲基丙烯酰氧基丙基三甲氧基硅烷（KH570）改性纳米二氧化硅（SiO2）,然后通过乳液聚合接枝上聚甲基丙烯酸甲酯（PMMA）,再将其与甲基丙烯酸甲酯（MMA）改性的天然胶乳,通过胶乳共混法制备天然橡胶／二氧化硅纳米复合材料,结果显示,纳米二氧化硅表面接枝上了PMMA,二氧化硅在橡胶基体中分散良好,粒径在60～100nm之间,得到的胶膜力学性能有很大的提高。     

Intercalated clays from pentaerythritol stearate for use in polymer nanocomposites

Smectite clays treated with quaternary ammonium salts have been utilized for decades in paints, greases, cosmetics, and personal care products as rheological modifiers. They have also been used in industrial wastewater treatment extensively. In more recent times these surface modified clays have demonstrated benefits in polymer/clay nanocomposites. The use of quaternary ammonium modifiers limits the usefulness of these composites in food packaging because they are not approved for direct food contact. It would be advantageous to have surface modifying chemicals acceptable for direct food contact in these composites. This article reports research conducted on a promising surface modifier pentaerythritol stearate (PS), which is approved by the FDA for inclusion in food as a preservative. The surface modification of montmorillonite with PS is reported in detail as well as the production of nanocomposites with selected polymers made with the modified clay. Molecular modeling and purification of commercial PS samples indicate that the mono‐ and diesters are the critical surface modifiers, although the as received commercial material works well in forming intercalated clay complexes. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

HMT增强丁苯橡胶力学性能的研究

通过对蒙脱土提纯,制得平均直径为2μm、蒙脱石质量分数为95％的片层状颗粒,经有机改性制得改性蒙脱土,并按m（环烃基油）：m（改性蒙脱石）=3：1的比例进行混合,制得橡胶增强剂——HMT。HMT增强丁苯橡胶实验结果表明,HMT最佳添加量为2～5份,丁苯橡胶的拉伸强度、定伸强度、撕裂强度等性能指标分别提高12．9％、4．6％、16．9％。