聚氨酯/有机蒙脱土纳米复合材料的结构与性能Ⅰ.水基端羟基阳离子聚氨酯改性蒙脱土

合成了一系列不同相对分子质量的水基端羟基阳离子聚氨酯(WHTCPU),用其作为插层剂对蒙脱土(MMT)进行有机改性,通过阳离子交换得到含有活性羟基官能团的有机MMT。用广角X射线衍射、傅里叶变换红外光谱、透射电子显微镜、原子吸收光谱和显微电泳法等对改性后MMT的结构、性能进行了分析表征。结果表明,经WHTCPU改性的MMT是含有活性羟基官能团的有机MMT;当NCO/OH的摩尔比为1.5/2时,MMT层间距由原来的1.264 nm扩大到2.025 nm,此时有机MMT的阳离子交换能最低;经过WHTCPU改性的MMT粒子的电性得到反转。     

季铵盐插层剂对高密度聚乙烯性能的影响

采用季铵盐阳离子作为插层剂与钠基蒙脱土层间的无机阳离子进行离子交换,制备系列有机化蒙脱土,利用红外光谱对蒙脱土的结构进行表征,结果表明,插层剂已进入蒙脱土的层间.同时将有机化蒙脱土与HDPE进行熔融插层,制备了纳米聚乙烯复合材料,研究了插层剂对其部分力学性能的影响.     

Preparation of organoclay by a precipitation–adsorption method

Organoclay was prepared by a precipitation–adsorption process in which sodium‐montmorillonite (Na‐MMT) suspension was fully mixed with an anionic surfactant, sodium dodecylbenzene sulfonate, and then precipitation agent CaCl₂ was added to produce a precipitate of organophilic montmorillonite (OMMT). The Na‐MMT suspension was obtained by ion‐exchange reaction of bentonite with sodium cation resin. Fourier transform infrared spectroscopy spectral analysis confirmed the adsorption of organic groups on the MMT, and the organic groups content was calculated from the results of thermal gravimetric analysis. X‐ray diffraction results indicated that the OMMT prepared was exfoliated. In this article, the mechanism of the precipitation–adsorption process was discussed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

改性剂种类对蒙脱土结构和性能的影响

为增加蒙脱土(montmorillonite,MMT)和有机物的相容性和研究插层剂种类对MMT结构和性能的影响,采用Cu,Co和Ni无机金属阳离子,十二烷基磺酸钠、十二烷基硫酸钠、α-烯烃磺酸盐和十二烷基苯磺酸钠等有机阴离子表面活性剂及十六烷基氯化吡啶、十六烷基三甲基溴化铵、十二烷基三甲基溴化铵等有机阳离子表面活性剂作为改性剂,对蒙脱土进行一次改性和二次改性,制备出一系列改性蒙脱土.研究了改性剂种类、插层方式、插层次序对插层效果的影响.X射线衍射分析表明:一次改性时,插层剂均能进入蒙脱土的层间,改性土的层间距由1.04nm增加到1.7～3.52nm;二次改性时,先阳离子后阴离子的插层顺序有利于层间距增大(4.14nm),还可利用配位作用将二次改性剂引入金属离子一次改性MMT中,使层间距增大.改性机理研究认为:阳离子改性机理为层间离子交换,而阴离子改性机理是改性剂和MMT表面形成了氢键.沉降实验表明一次改性土和二次改性土在有机溶剂中分散能力有所增强.     

Polypropylene nanocomposites prepared with natural and ODTABr‐modified montmorillonite

In this study, the main goal is to obtain montmorillonite nanocomposites of polypropylene (PP). To achieve this goal, a two‐phase study was performed. In the first part of the work, organomodified clay (OMMT) was synthesized and characterized. Octadecyltrimethylammonium bromide (ODTABr) cationic surfactant was added to the clay (Na‐activated montmorillonite, MMT) dispersions in different concentrations in the range of 5 × 10^?5–1 × 10^?2 mol/L. Rheologic, electrokinetic, and spectral analyses indicated that ODTABr has interacted with MMT at optimum conditions when the concentration was 1 × 10^?2 mol/L. In the second part, modified (OMMT) and unmodified (MMT) montmorillonite were used to obtain PP nanocomposites (OMMT/PP and MMT/PP, respectively). The nanocomposites were prepared by melt intercalation where the montmorillonite contents were 1 or 5% (w/w) for each case. The thermal analyses showed that the thermal properties of OMMT/PP nanocomposites were better than MMT/PP, and both of them were also better than pure polymer. Increase in the concentration of MMT (or OMMT) decreased the thermal resistance. Based on the IR absorption intensity changes of regularity and conformational bands, it is found that the content of the helical structure of macromolecular chains has increased with increasing concentrations of both MMT and OMMT in the nanocomposites. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Modification of montmorillonite with cationic surfactants. Thermal and chemical analysis including CEC determination

The thermal stability of synthesized and commercial organically modified montmorillonites has been investigated using thermogravimetric analysis (TGA). Four organo-montmorillonites have been prepared by replacing the inorganic cations of a commercial montmorillonite with aliphatic and aromatic ammonium bromide or chloride salts. The modification has been carried out by cation exchange to obtain a high level of intercalation in the montmorillonite. Conformations of the intercalated surfactants have been characterized using Fourier transform infrared spectroscopy (FTIR). Besides fixed organic surfactant, some surfactant in excess still remained in the montmorillonite after repeated washing with water or ethanol/water. The use of a suitable eluent for the surfactants in the washing step was the key issue as shown by the changes of the first degradation peak of Cloisite-Na⁺-hexadecyl benzyl dimethylammonium (CLO-BDHA), Cloisite-Na⁺-benzyl triethylammonium (CLO-BTA) and Cloisite-Na⁺-hexadecyl trimethylammonium (CLO-HTA). Hexadecyl trimethylammonium (HTA) was more sensitive to water and ethanol/water as eluents. Sonication and the use of a polar activator during the modification of montmorillonite increased the amount of surfactant adsorbed by cation exchange. Ammonium acetate method has been revealed as an adequate chemical method to measure the cation exchange capacity (CEC) of inorganic and organic montmorillonites. This method has the advantage with respect to TGA that it does not measure the unfixed surfactant.     

Exfoliation of organically modified montmorillonite driven by molecular diffusion in maleated polypropylene

This work is focused on the factors influencing the intercalation of maleated polypropylene (PPMA) into organically modified montmorillonite (OMMT). Two kinds of PPMA were used to explore the optimal candidate for effective intercalation into OMMT. The grafting degree of maleic anhydride and the viscosity of PPMA have effects on the diffusion of polymer molecules. Moreover, the loading level of surfactant was varied to optimize the modification of montmorillonite because the appropriate loading level can provide a balance between interlayer distance and steric hindrance. The kind of surfactant changes the interaction between OMMT and PPMA, and accordingly the intercalation of PPMA is different, resulting in the discrepancy of the intercalation of PPMA. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

有机蒙脱土对单宁酸的吸附性能

利用十六烷基二甲基羟乙基溴化铵对钠基蒙脱土（MMT）进行离子交换改性,制得有机蒙脱土（OMMT）,并通过FT-IR、XRD对MMT改性前后的结构进行表征。通过静态吸附试验,探究OMMT对单宁酸（TA）的吸附条件和吸附机理。结果表明,OMMT吸附TA对pH值有较大的依赖性,吸附最佳pH值在4.0左右;吸附平衡时间为6h,吸附动力学曲线符合准二级动力学模型;吸附等温线用Langmuir方程比Freundlich方程能更好地描述;在pH值为4.0、TA初始浓度为500 mg/L、温度为20℃时,最大吸附容量为181.6mg/g;热力学参数ΔG、ΔH均为负值表明吸附为自发的放热过程。在饱和吸附和解吸重复7次后,再生OMMT吸附容量下降不到20%。     

蒙脱土的有机化改性及插层剂的选择

分别利用阳离子表面活性剂十六烷基三甲基氯化铵(CTAC)和阴离子表面活性剂十二烷基磺酸钠(SDS)制备了有机蒙脱土,并通过FTIR和XRD对其结构进行表征,发现CTAC的插层效果明显优于SDS。研究中考察了体系反应温度、pH值对蒙脱土插层效果的影响。结果表明,以CTAC为插层剂,反应时间为1 h,反应温度为80℃,体系pH值为7时,制得的有机蒙脱土其d001值达1.962 nm,层间距最大。     

Processing thermal stability and degradation kinetics of poly(vinyl chloride)/montmorillonite composites

Thermal stability of polyvinyl chloride (PVC) based montmorillonite composites with either sodium montmorillonite (MMT) or alkyl ammonium ion modified montmorillonite (OMMT) were investigated by thermogravimetric analysis. The apparent activation energies associated with the first thermal degradation stage were calculated by the methods of Flynn–Wall–Ozawa and Kissinger in nitrogen atmosphere at several different heating rates. The processing thermal stability of PVC and PVC/MMT(OMMT) composites was also discussed. Increase of mixing torque did not result in a larger intercalation extent of PVC on MMT; instead, it unexpectedly induced discoloration of PVC and then deteriorated the processing stability, especially in the presence of OMMT. The apparent activation energies in the first thermal degradation stage exhibited little difference among PVC, PVC/MMT, and PVC/OMMT composites, and the kinetic compensation effect of S_p^* kept a constant value, indicating that the thermal stability and thermal degradation mechanism of PVC were not affected by the presence of either MMT or OMMT, although the processing discoloration of PVC is observed for PVC/OMMT composite. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1521–1526, 2004     

不饱和阳离子水性聚氨酯改性蒙脱土的制备与性能研究

合成出一种不饱和水基阳离子聚氨酯树脂（UCWPU）,以其作为插层剂并采用超声波助混技术对蒙脱土（MMT）进行有机改性,通过阳离子交换制备出含有不饱和官能团的活性有机蒙脱土（OMMT）。采用傅里叶变换红外光谱（FTIR）、广角X射线衍射（XRD）、透射电镜（TEM）、热失重分析（TGA）和显微电泳法等检测手段分别对改性后蒙脱土的结构、性能进行了分析表征。结果表明,改性后的蒙脱土层间距由原来的1．21nm增大到2．13nm,阳离子聚氨酯改性的蒙脱土粒子电性显正电。FT—IR和TGA测试结果表明UCWPU分子链稳定存在于蒙脱土层问。     

SEBS/蒙脱土复合材料结构及热性能研究

采用十二烷基三苯基溴化膦(DTPB)改性钠基蒙脱土(Na+-MMT),利用熔融插层法制备氢化苯乙烯-丁二烯-苯乙烯嵌段共聚物(SEBS)/蒙脱土复合材料。采用X射线衍射仪、红外光谱仪、场发射扫描电镜、热重分析仪对样品进行结构表征和性能测试,比较不同有机化蒙脱土(OMMT)对SEBS/OMMT复合材料的影响。结果表明:无论是MMT还是OMMT都起到了阻止SEBS热失重进程的发展,且携带苯基的DTPB有机改性剂有利于OMMT与SEBS复合材料的相容性。     

有机MMT对高密度聚乙烯改性的研究

采用十二烷基三甲基氯化铵、十六烷基三甲基氯化铵、十六烷基三甲基溴化铵和双十八烷基二甲基氯化铵4种阳离子表面活性剂对钠基蒙脱土(MMT)进行有机化处理,制备了有机MMT(OMMT)。将OMMT与高密度聚乙烯(HDPE)进行熔融插层制备了HDPE／OMMT纳米复合材料,研究了OMMT的层间距同季铵盐烷基链的关系。结果表明,OMMT的层间距随烷基链长度的增加而增大;随着OMMT含量的增加,HDPE／OMMT纳米复合材料的断裂伸长率和拉伸强度降低,弯曲弹性模量增加,弯曲强度出现极大值,使该纳米复合材料的力学性能得到了一定的改善。     

改性剂及高密度聚乙烯插层和剥离蒙脱石的分子动力学模拟

为研究高密度聚乙烯/有机改性蒙脱石(PE-HD/OMMT)复合材料中改性剂及PE-HD对蒙脱石(MMT)插层和剥离的影响,采用分子动力学方法模拟了OMMT中不同负载量的十八烷基三甲基氯化铵阳离子(OTAC+)在MMT中的排列方式以及对MMT插层的影响.此外,搭建了PE-HD/OMMT复合材料模型,编写MS Perl脚本...     

The effect of clay modification on the mechanical properties of poly(methyl methacrylate)/organomodified montmorillonite nanocomposites prepared by in situ suspension polymerization

Poly(methylmethacrylate) (PMMA)/montmorillonite (MMT) nanocomposites were prepared by in situ suspension polymerization. MMT was previously organically modified by different modification agents [dioctadecyl dimethyl ammonium chloride (DODAC) and methacrylatoethyltrimethyl ammonium chloride (MTC)] and different modification method (cation‐exchange reaction and grafting reaction), ultimately giving rise to five kinds of organomodified MMT (OMMT). The structure of the OMMT was studied by Wide angle X‐ray diffraction (WAXD) and Fourier transform infrared spectroscopy (FTIR). Meanwhile, the structure of the PMMA/MMT nanocomposites microspheres was also investigated by WAXD. The molecular weight of the polymers extracted from PMMA/MMT nanocomposites was measured by gel permeation chromatograph (GPC). Finally, the mechanical properties of these PMMA/MMT nanocomposites were studied in detail. It was found that large interlayer spacing (d₀₀₁) of OMMT could not entirely ensure an exfoliated structure of resultant PMMA/MMT nanocomposites, while OMMT with relative small d₀₀₁ could still yield exfoliated structure as long as the compatibility between OMMT and polymer matrix was favorable. In addition, the results of mechanical investigation indicated that the compatibility between OMMT and PMMA matrix turned out to be the dominant factor deciding the final mechanical properties of PMMA/MMT nanocomposites. POLYM. COMPOS., 37:1705–1714, 2016. © 2014 Society of Plastics Engineers     

Preparation of nanocomposite by adding of Tunisian nanoclay in unsaturated polyester matrix: mechanical and thermal study

Unsaturated Polyester (UP) resin is widely used for many applications such as reinforced plastic (FRP) and polymer composites. However, these materials suffer from their low mechanical and thermal properties. For enhancing their performance, researchers have used Tunisian montmorillonite (MMT) for manufacturing of unsaturated polyester-montmorillonite (UP-MMT) nanocomposite synthesized by dispersing the UP resin into the silicate layers of MMT. The MMT has been modified ammonium quaternary as organic cation (OMMT). Test results, supported by mechanical testing, X-ray diffraction, thermal analysis (DSC and TGA) and transmission electron microscopy, indicated that the mechanical properties and the thermal stability of unsaturated polyester with OMMT nanocomposite (UP/OMMT) are better than those of pure UP. The degradation temperature increased by 78 °C with the addition of organic modification, and SEM micrographs show good dispersion of modified montmorillonite in the polymer matrix. Tensile strength is increased by 81 % for the UP/OMMT nanocomposite.     

有机蒙脱土的制备及表征

采用插层剂十六烷基三甲基溴化铵(1631-Br)与蒙脱土层问的阳离子进行交换,优化反应条件(插层剂用量、改性时间)分别制备了不同的有机蒙脱土并将其用X射线衍射,红外光谱和透射电镜进行测试,结果表明,加入饱和插层量25%的插层剂搅拌2 h即可制备能较大幅度改进高聚物与沥青相客性的有机蒙脱土材料.     

聚丙烯/蒙脱土纳米复合材料的制备与性能研究

采用十八烷基三甲基氯化铵（OTAC）和十二烷基二甲基卞基氯化铵（DDBAC）改性蒙脱土,以聚丙烯接枝马来酸酐（PP-g-MAH）作相容剂,通过熔融插层法制备了聚丙烯/蒙脱土纳米复合材料（PP/OMMT）.结果表明,PP-g-MAH能有效地改善PP与OMMT的相容性,当OTAC改性的蒙脱土（OMMT-O）用量为5wt%、PP-g-MAH用量为10wt%时,PP/PP-g-MAH/OMMT-O纳米复合材料的冲击强度为5.4 KJ/m^2,比纯PP提高了80%,极限氧指数（LOI）由PP的18提高到23.X射线衍射（XRD）测试表明,PP已经插层进入到蒙脱土片层中,部分蒙脱土产生了剥离.     

三聚氰胺磷酸盐改性蒙脱土的合成

分别将三聚氰胺磷酸盐(MP)插层进蒙脱土(MMT)和有机化蒙脱土(OMMT)中,制得改性产物MP-MMT和MP-OMMT。通过红外(IR)、X-射线衍射(XRD)及扫描电镜(SEM)对制得的样品进行表征。结果表明;MP可对MMT和OMMT进行改性在MP用量不变的情况下MP对MMT的改性效果好于OMMT。     

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。