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.     

Transport properties of natural rubber latex layered clay nanocomposites

Natural rubber latex layered clay nanocomposites were prepared with low loadings of nanoclay using conventional compounding technique. A higher loading of clay resulted in processing difficulties due to viscosity build up. X‐ray analysis showed that nanocomposites in which layered silicate layers were either delaminated or ordered as in an intercalated structure was obtained. Partially exfoliated structure was observed from TEM photographs of nanocomposites with 3 phr nanoclay. The transport properties, sorption, diffusion, and permeation coefficients were measured using the solvent toluene at 303 K. A higher decrease for the diffusion coefficient for nanocomposites directs the presence of tortuous path for the diffusing molecules. Thermodynamic parameters show a better compatibility for the silicates with rubber resulted in the formation of an elastomeric network. Gas permeability results of the nanocomposites suggest a better barrier resistancefor oxygen molecules even in lower loading of nanoclay and different gas transport models (Nielsen, Bharadwaj, Cussler) were applied to describe the behavior of these nanocomposites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

黏土/天然橡胶纳米复合材料在矿用轮胎胎面胶中的应用

用黏土/天然橡胶纳米复合材料代替部分进口天然橡胶和炭黑制备抗崩花掉块和耐破坏的高性能的矿山轮胎胎面胶。结果表明,纳米黏土基本不影响胶料的硫化性能;纳米黏土构建网络结构的能力较强,Payne效应明显,黏土复合体系的混炼胶具有较好的挺性,硫化胶具有较高的硬度和定伸应力;纳米黏土片层能够沿外力方向取向并诱导高分子链取向,黏土复合体系的断裂伸长率较高,拉伸强度和撕裂强度较大,生热较高,同时纳米黏土的片层结构能够钝化支化裂纹尖端,复合体系的耐切割和耐屈挠裂纹增长性能优异。成品轮胎的路试结果表明,黏土/天然橡胶纳米复合材料完全可以代替进口天然橡胶用于矿山专用全钢载重子午线轮胎胎面胶配方中。     

黏土/天然橡胶纳米复合材料的制备及性能

利用乳液插层法制备了黏土／天然橡胶纳米复合材料,研究了该复合材料的力学性能、应力应变行为、耐磨性、气体阻隔性和耐老化性能。结果表明,黏土／天然橡胶纳米复合材料与高耐磨炭黑(N330)、白炭黑增强橡胶相比,邵尔A型硬度、定伸应力和撕裂强度较高,拉伸强度相当。黏土、N330以及白炭黑对天然橡胶的拉伸结晶有影响,填料用量对材料拉伸强度的影响存在最佳值。黏土／天然橡胶纳米复合材料具有良好的耐磨性、气体阻隔性和耐老化性能。     

Morphology and mechanical properties of clay/styrene‐butadiene rubber nanocomposites

Based on the character of a clay that could be separated into many 1‐nm thickness monolayers, clay styrene‐butadiene rubber (SBR) nanocomposites were acquired by mixing the SBR latex with a clay/water dispersion and coagulating the mixture. The structure of the dispersion of clay in the SBR was studied through TEM. The mechanical properties of clay/SBR nanocomposites with different filling amounts of clay were studied. The results showed that the main structure of the dispersion of clay in the SBR was a layer bundle whose thickness was 4–10 nm and its aggregation formed by several or many layer bundles. Compared with the other filler, some mechanical properties of clay/SBR nanocomposites exceeded those of carbon black/SBR composites and they were higher than those of clay/SBR composites produced by directly mixing clay with SBR through regular rubber processing means. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1873–1878, 2000     

Impact of curing temperature on microstructures and properties of isobutylene–isoprene rubber/clay nanocomposites

In this work, the influence of curing temperature on microstructures of isobutylene–isoprene rubber/clay nanocomposites (IIRCNs) prepared by melt compounding was characterized using wide‐angle X‐ray diffraction and TEM. The gas barrier and tensile properties of IIRCN cured under different temperature were examined. The results reveal that high pressure, curing reactions, and reactions of amine intercalants with curing agents together play important roles on determining the final microstructures of cured IIRCNs. Changing curing temperature would dramatically alter intercalated structure, dispersion homogeneity, filler–rubber interaction strength, and crosslinking density of obtained IIRCN, resulting in great difference in final properties. Finally, some suggestions for the preparation of successful RCNs were proposed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of surface modification of silicon carbide nanoparticles on the properties of nanocomposites based on epoxidized natural rubber/natural rubber blends

Improvement of the properties of rubber nanocomposites is a challenge for the rubber industry because of the need for higher performance materials. Addition of a nanometer‐sized filler such as silicon carbide (SiC) to enhance the mechanical properties of rubber nanocomposites has rarely been attempted. The main problem associated with using SiC nanoparticles as a reinforcing natural rubber (NR) filler compound is poor dispersion of SiC in the NR matrix because of their incompatibility. To solve this problem, rubber nanocomposites were prepared with SiC that had undergone surface modification with azobisisobutyronitrile (AIBN) and used as a filler in blends of epoxidized natural rubber (ENR) and natural rubber. The effect of surface modification and ENR content on the curing characteristics, dynamic mechanical properties, morphology and heat buildup of the blends were investigated. The results showed that modification of SiC with AIBN resulted in successful bonding to the surface of SiC. It was found that modified SiC nanoparticles were well dispersed in the ENR/NR matrix, leading to good filler‐rubber interaction and improved compatibility between the rubber and filler in comparison with unmodified SiC. The mechanical properties and heat buildup when modified SiC was used as filled in ENR/NR blends were improved. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45289.     

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     

Study of the preparation of silicone rubber particles with core–shell structure by seeded emulsion polymerization

Silicone rubber particles with core–shell structure were prepared by polymerization of vinyl monomers in the presence of linear or cross-linked poly(dimethyl siloxane–methyl vinyl siloxane) latexes. The monomers were added in either continuous or swelled-continuous modes. Core–shell particles with poly(butyl methacrylate), or poly(methyl methacrylate), as the shell were obtained by using either addition mode. The core–shell structure was not observed for polysiloxane–polystyrene particles. The influence of monomer addition mode, the compatibilities of the monomers and their homopolymers with silicone rubber, and the reactivity ratios of the vinyl monomers with the vinyl group of linear polysiloxane particles, on the formation of the core-shell structure is discussed.     

工程轮胎胎面胶用黏土/炭黑/天然橡胶纳米复合材料的性能

在工程轮胎胎面胶配方中,用黏土替代部分高耐磨炭黑,利用机械共混工艺制备了黏土/炭黑/天然橡胶(NR)纳米复合材料,研究了复合材料的综合性能.结果表明,黏土的加入不会对胶料的硫化特性产生太大影响;少量黏土的加入增强了混炼胶的填料网络作用,改善了炭黑/NR硫化胶的物理机械性能,耐磨性能提高了15%～30%,降低了滚动阻力,提高了耐屈挠疲劳破坏性能,当黏土填充量为4份时,复合材料的综合性能最优.     

Styrene–butadiene rubber/cellulose II/clay nanocomposites prepared by cocoagulation—mechanical properties

In this work, nanocomposites of styrene butadiene rubber (SBR), cellulose II, and clay were prepared by cocoagulation of SBR latex, cellulose xanthate, and clay aqueous suspension mixtures. The incorporated amount of cellulose II was 15 phr, and the clay varied from 0 to 7 phr. The influence of cellulose II and clay was investigated by rheometric, mechanical, physicochemical, and morphological properties. From the analysis of transmission electron microscopy (TEM), dispersion in nanometric scale (below 100nm) of the cellulosic and mineral components throughout the elastomeric matrix was observed. XRD analysis suggested that fully exfoliated structure could be obtained by this method when low loading of silicate layers (up to 5 phr) is used. The results from mechanical tests showed that the nanocomposites presented better mechanical properties than SBR gum vulcanizate. Furthermore, 5 phr of clay is enough to achieve the best tensile properties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

橡胶／粘土插层纳米复合材料的研究进展

综述了橡胶／粘土插层纳米复合材料的制备方法及性能特征。重点介绍了溶液插层法、乳液插层法和熔体插层法及相关研究进展。评价了各种制备技术的优缺点,提出了橡胶／粘土插层纳米复合材料的发展趋势。     

用附着型促进剂制备橡胶/蒙脱土纳米复合材料

用附着型促进剂PBS在机械混炼插层法的基础上制备了天然橡胶/蒙脱土纳米复合材料。由于硫化后大部分促进剂基团都连在橡胶分子链上,因此用分子一端能和蒙脱土片层有相互作用的附着型硫化促进剂,可以大大增强蒙脱土和橡胶基体的相互作用,得到性能优良纳米复合材料。用PBS制备纳米复合材料其硫化体系活性能低,硫化胶交联密度增大,有机蒙脱土片层在橡胶基体中达到纳米级的分散,具有优良的力学性能,加入8%有机蒙脱土100%模量从1.2 MPa增至2.2 MPa,500%模量从8.12 MPa增至18.23 MPa,邵氏GA硬度从45增至55,而加入2%有机蒙脱土500%模量从8.12 MPa增至17.06 MPa,撕裂强度从36.31 kN/m增至43.65kN/m,加入2~10份有机蒙脱土时其效果相当于加入40份半补强炭黑。     

Effect of interfacial attraction on intercalation in polymer/clay nanocomposites

In order to examine the adhesive behavior of a polar polymer between hydrophilic clay layers, the so‐called glue effect, a clay intercalation by an ethylene–vinyl alcohol (EVOH) copolymer, which was capable of strong hydrogen bonding with the silicate surface of clay, was prepared by the melt intercalation technique and compared with a clay nanocomposite containing styrene–acrylonitrile (SAN) copolymer of less polar interaction energy in terms of the morphology and mechanical properties. Although initial penetration of the guest polymer into the gallery of the host clay occurred more rapidly for EVOH because of its strong hydrophilic nature, the dissociation of clay nanoplatelets was better developed for SAN with less polar interaction with clay, well evidencing the fact that the glue effect effectively affects the intercalation behavior of polymer/clay nanocomposites. However, the mechanical properties of the EVOH/clay nanocomposite were superior to those of SAN/clay nanocomposites. Although dissociation of respective silicate layers was poor for EVOH/clay nanocomposites, strong attractive energy stabilizes the interface between inorganic nanoparticles and the polymer matrix much more effectively, resulting in higher mechanical properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2749–2753, 2006     

Physical properties of natural rubber/organoclay nanocomposites compatibilized with epoxidized natural rubber

Onium ion‐modified montmorillonite (organoclay) was melt 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) was used in 10 parts per hundred rubber (phr) as a compatibilizer. The effect of organoclay with different filler loading up to 10 phr was studied. Cure characteristics were determined by a Monsanto MDR2000 rheometer, whereas the tensile, compression, and tear properties of the nanocomposites were measured according to the related ASTM standards. While the torque maximum and torque minimum increased slightly, both scorch time and cure time reduced with the incorporation of organoclay. The tensile strength, elongation at break, and tear properties went through a maximum (at about 2 phr) as a function of the organoclay content. As expected, the hardness, moduli at 100% (M100) and 300% elongations (M300) increased continuously with increasing organoclay loading. The compression set decreased with incorporation of organoclay. The dispersion of the organoclay in the NR stocks was investigated by X‐ray diffraction and transmission electron microscopy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1083–1092, 2006     

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。     

Melt‐compounded natural rubber nanocomposites with pristine and organophilic layered silicates of natural and synthetic origin

Composites based on natural rubber (NR) and containing organophilic and pristine layered silicates of natural and synthetic origin were produced by melt compounding and sulfur curing. The curing, thermomechanical, and mechanical properties of the mixes, which contained 10 phr (parts per hundred parts of rubber) silicates, were determined. The dispersion of the silicates was studied by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Organophilic clays accelerated the sulfur curing of NR, which was believed to occur because of a complexation reaction in which the amine groups of the clay intercalants participated. The property improvements caused by the fillers were ranked as follows: organophilic clays > pristine synthetic layered silicate (sodium fluorohectorite) > pristine natural clay (purified sodium bentonite) > precipitated nonlayered silica (used as a reference). This was attributed to partial intercalation of the organophilic clay by NR on the basis of XRD and TEM results and to the high aspect ratio of the fluorohectorite. Apart from intercalation, severe confinement (i.e., the collapse of the interlayer distance) of the organoclays was observed. This peculiar feature was traced to the formation of a zinc coordination complex, which extracted the amine intercalant of the organoclays, thus causing the collapse of the layers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 813–819, 2004     

Preparation and characterization of rubber–clay nanocomposites

Rubber–clay nanocomposites were prepared by two different methods and characterized with TEM and XRD. The TEM showed clay had been dispersed to one or several layers. The XRD showed that the basal spacing in the clay was increased. It was evident that some macromolecules intercalated to the clay layer galleries. The clay layer could be uniformly dispersed in the rubber matrix on the nanometer level. The mechanical tests showed that the nanocomposites had good mechanical properties. Some properties exceeded those of rubber reinforced with carbon black, so the clay layers could be used as an important reinforcing agent as the carbon black was. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1879–1883, 2000     

Synthesis and characterization of in situ sodium‐activated and organomodified bentonite clay/styrene–butadiene rubber nanocomposites by a latex blending technique

In this article, we describe a method used to prepare an in situ sodium‐activated, organomodified bentonite clay/styrene–butadiene rubber nanocomposite master batch via a latex blending technique. The clay master batch was used for compound formulation. Octadecyl amine was used as an organic intercalate. The clay was purchased from local suppliers and was very cheap. Sodium chloride was used for in situ activation of the clay. The wide‐angle X‐ray diffraction data indicated that the in situ sodium activation helped to increase the intergallery distance from 1.28 to 1.88 nm. A transmission electron micrograph indicated intercalation and partial exfoliation. The thermal properties were relatively better in the case of the sodium‐activated, organomodified bentonite‐clay‐containing compound. A substantial improvement in physical properties such as the modulus, tensile strength, tear strength, and elongation at break was observed in the case of the in situ sodium‐activated compound. A cation‐exchange capacity equivalent (of the clay) of 1.5 times the octadecyl amine was the optimum dose for the modification. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

硫化方法对橡胶/黏土纳米复合材料黏土片层分散状态的影响

通过熔体插层法以及常压硫化法制备了橡胶/黏土纳米复合材料,并与模压硫化法制备的复合材料进行了对比,研究了硫化方法对橡胶/黏土纳米复合材料微观分散状态的影响。结果表明:采用熔体插层法制备的橡胶/黏土混合物,其受限状态的橡胶大分子链在高温、高压条件下,在黏土片层之间处于一种热力学不稳定状态;模压处理会对橡胶/黏土混合物的分散状态产生不利影响。透射电子显微镜和X光衍射分析表明,采用模压硫化、常压硫化得到的丁基橡胶或丁苯橡胶/黏土纳米复合材料中黏土片层的微观分散状态不同;排除压力的影响,常压硫化有利于提高橡胶/黏土纳米复合材料中黏土片层的分散程度。