季铵盐插层钠基蒙脱土的工艺研究

采用溴化十六碳烷基三甲铵对钠基蒙脱土进行改性,研究了反应温度、反应配比、反应时间和搅拌方式对蒙脱土插层效果的影响。FTIR证明有机插层剂已进入蒙脱土的层间;XRD结果表明蒙脱土的层间距由1．4nm增加到2．8～3．9nm;TEM观察表明蒙脱土的层间距增大。     

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。     

蒙脱土的有机化改性及其结构与性能研究

采用十八烷基三甲基溴化铵、双羟乙基十二烷基三甲基氯化铵和含氢硅油三种不同有机插层剂对无机蒙脱土进行有机化改性。采用FTIR、XRD、BET以及TGA分析了有机蒙脱土的结构与性能。结果表明,不同种类的有机插层剂对蒙脱土的层间距、比表面积以及热稳定性均有不同程度的提高,其中,含氢硅油对于上述结构与性能的提高最为显著。     

复合插层有机蒙脱土的制备及表征

以钠基蒙脱土、十六烷基三甲基溴化铵(CTAB)和己内酰胺为原料,制备了复合插层有机蒙脱土。红外光谱分析(IR)、热重分析(TGA)和X-射线衍射分析(XRD)表明,有机插层剂已进入蒙脱土的层间,CTAB/己内酰胺复合插层有机蒙脱土的层间距大于单阳离子CTAB插层有机蒙脱土的层间距。Molau实验结果表明,这种有机蒙脱土在有机介质中表现出很好的分散性。     

DODAC对水热法插层改性蒙脱土结构和性能的影响

选用阳离子表面活性剂双十八烷基二甲基氯化铵(DODAC)作为改性剂,通过水热法插层改性钠基蒙脱土(Na-MMT).采用傅里叶变换红外光谱(FT-IR)、X射线衍射(XRD)、热重分析(TGA)、扫描电镜(SEM)等手段研究了水热插层法和DODAC添加量对有机化蒙脱土结构和性能的影响.研究结果表明:水热法的插层改性效果优于常规插层改性方法,DODAC添加量对有机化蒙脱土的层间结构影响显著,随改性剂添加量增加,有机化蒙脱土的层间距变大,DODAC分子的层间堆叠方式依次由单层、双层向伪三层、类石蜡复合型结构转变.当DODAC添加量为2.0CEC时,水热插层改性效果最为明显.     

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.     

二聚阳离子表面活性剂改性蒙脱土的制备和表征

合成了二聚阳离子表面活性剂GeminiC12,用核磁共振氢谱(1HNMR)表征了它的结构,并用它作为有机插层剂应用于蒙脱土的改性处理。红外光谱(FTIR)、热重分析(TGA)表明,GeminiC12已插层到蒙脱土片层间。X射线粉末衍射(XRD)表明,插层后蒙脱土层间距从1 19nm增加到3 8nm,是十六烷基三甲基溴化铵(CTAB)处理效果的两倍。沉降实验表明,改性后蒙脱土在苯乙烯和石蜡中形成凝胶体系,表现出很好的相容性和分散性,这种改性效果优于目前常用的CTAB处理效果,更有利于聚合物或其单体进入蒙脱土层间形成纳米复合材料。     

机械化学法有机插层改性蒙脱土的研究

采用机械化学法对蒙脱土进行有机插层改性,研究了固含量、反应时间、醇水比、改性剂的加入量、研磨时间等因素的影响。结果表明,在体系固含量为35%、反应时间0.5h、醇水比为1:8、加入1.0CEC的改性剂可使其层间距从钠化后的1.2nm提高到约2.0nm,且片层结构规则;短时间的研磨有利于提高改性蒙脱土的层间有序性,延长时间则会破坏其片层结构。     

蒙脱土结构和性质对催化不饱和脂肪酸二聚化反应的影响

钠基蒙脱土经过一次插层有机改性和二次插层有机改性后制得有机改性蒙脱土,作为催化剂用于催化不饱和脂肪酸二聚化反应制备二聚酸。采用XRD、SEM、TEM、FTIR和TG等检测手段对有机改性后蒙脱土的内层结构和性质进行分析。实验表明改性后蒙脱土层间距由1.48 nm扩大到3.82 nm,而且保持原来的夹心结构不变。蒙脱土的表面形貌和内部结构发生改变,表面变得疏松,内部层间距扩大且插层剂含量增加,分散实验表明二次插层有机改性蒙脱土在不饱和脂肪酸中分散性能优异。相同条件下,二次插层有机改性蒙脱土催化不饱和脂肪酸二聚化反应,二聚酸产率75.33%,是未改性蒙脱土催化制得二聚酸产率的2.14倍,并通过FTIR、¹H NMR和LC-MS证实合成的产物为二聚酸。     

蒙脱土结构和性质对催化不饱和脂肪酸二聚化反应的影响

钠基蒙脱土经过一次插层有机改性和二次插层有机改性后制得有机改性蒙脱土,作为催化剂用于催化不饱和脂肪酸二聚化反应制备二聚酸。采用XRD、SEM、TEM、FTIR和TG等检测手段对有机改性后蒙脱土的内层结构和性质进行分析。实验表明改性后蒙脱土层间距由1.48nm扩大到3.82nm,而且保持原来的夹心结构不变。蒙脱土的表面形貌和内部结构发生改变,表面变得疏松,内部层间距扩大且插层剂含量增加,分散实验表明二次插层有机改性蒙脱土在不饱和脂肪酸中分散性能优异。相同条件下,二次插层有机改性蒙脱土催化不饱和脂肪酸二聚化反应,二聚酸产率75.33%,是未改性蒙脱土催化制得二聚酸产率的2.14倍,并通过FTIR、1 H NMR和LC-MS证实合成的产物为二聚酸。     

Effect of interlayer cations on exfoliating 2D montmorillonite nanosheets with high aspect ratio: From experiment to molecular calculation

In this work, the montmorillonite (MMT) with different interlayer ions (Na⁺ and Ca²⁺) were exfoliated to prepare high aspect ratio 2D montmorillonite nanosheets (MMTNS). The effect of interlayer cations was experimentally and theoretically studied through the atomic force microscope (AFM) and molecular simulation. Na-MMT could be more easily exfoliated to monolayer with the thickness of 0–1 nm compared to Ca-MMT, and the exfoliated Na-MMTNS have higher lateral diameter than Ca-MMTNS under the same condition, leading to that the Na-MMTNS with high aspect ratio can be more readily obtained. This observation was sufficiently interpreted by molecular dynamic simulation and first principles calculations including band structure, density of states, electron density difference and electron localization function. It is indicated that the interlayer binding energy of Na-MMT was weaker while its in-plane structure was stronger compared with Ca-MMT. The strong interacting force between interlayer Ca atoms and the in-plane atoms will cause structural failure after exfoliating Ca-MMT off to 2D nanosheets. It is suggested that the interaction between the extranuclear electrons of atoms in MMT layer and interlayer cations will affect the overall intensity and apparent exfoliation properties.     

Correlation of exfoliation performance with interlayer cations of montmorillonite in the preparation of two-dimensional nanosheets

Montmorillonite (MMT) can be exfoliated into nanosheets used in a wide range of applications as two-dimensional (2D) material. The exfoliated MMT nanosheets with high diameter–thickness ratio appear to show superior properties in preparation of nanocomposites and other functional materials. In this work, the correlation of exfoliation performance with interlayer cations of MMT in the preparation of 2D nanosheets was investigated. The thickness and lateral diameter of MMT nanosheets were quantitatively measured by atomic force microscopy (AFM) technique. AFM results showed the exfoliated K-MMT had larger lateral diameter and thinner thickness than the exfoliated Ca-MMT under the same exfoliation conditions. Molecular simulation was applied to investigate the interlayer-binding energy (IBE), population analysis and density of states. K-MMT structures tend to have higher in-plane chemical bond intensity than Ca-MMT because of the impact of antibonding. The IBE of K-MMT was higher than that of Ca-MMT after the sorption of water molecules into the neighboring monolayers, indicating that thinner naonosheets tend to be easier obtained from Ca-MMT than K-MMT in liquid exfoliation. These findings might be helpful for the preparation and application of 2D MMTNS through controlling interlayer cation species and the exfoliation properties of MMT.     

SYNTHESIS OF POLY(METHYL METHACRYLATE)—CLAY NANOCOMPOSITES

Poly(methyl methacrylate)/clay nanocomposites were synthesized via in situ free radical polymerization of methyl methacrylate (MMA) in the presence of functionalized clay. Montmoril-lonite (MMT), a smectic type of clay, was treated with a commercial cationic surfactant, benzalkonium chloride (BAC), and a synthesized zwitterionic surfactant, octadecyldimethyl betaine (CI8DMB) Functionalized MMT was prepared via an ion exchange between Na,ions in the clay and the surfactant cations in aqueous medium. The intercalation of the surfactant in the clay galleries was determined using X-ray diffraction (XRD). The interlayer spacing for C18DMB was 2.03nm, higher than 1.86nm observed for BAC. This is due to longer chain length of C18DMB. Both organophilic clays formed a viscous gel when dispersed in the monomer, MMA. Poly(methyl methacrylate) (PMMA) nanocomposites were obtained by polymerizing the dispersions. XRD and transmission electron microscopy (TEM) indicate predominant exfoliation of the silicate layers in the polymer matrix for MMT treated with C18DMB, and partial exfoliation for MMT treated with BAC     

聚己内酯/有机蒙脱土纳米复合材料的制备与性能表征

以十六烷基三甲基溴化铵(CTAB)为有机改性剂处理钠基蒙脱土(Na-MMT),制备了有机蒙脱土(CTAB-MMT),再以CTAB-MMT为插层剂,通过熔融挤出制备了聚己内酯(PCL)/CTAB-MMT纳米复合材料。采用SEM和XRD对MMT和纳米复合材料的结构进行了表征,并测试了纳米复合材料的力学性能。结果表明:CTAB-MMT的片层结构比Na-MMT连续性更好,片层间距由原来的1.51nm增加到1.95～3.32nm;CTAB-MMT在PCL基体中分散更均匀;与纯PCL相比,PCL/CTAB-MMT纳米复合材料的拉伸强度提高了10.2%,而弯曲强度提高了19.5%。     

不同表面活性剂制备有机蒙脱土

分别利用阳离子表面活性剂十六烷基三甲基溴化铵、十六烷基三甲基氯化铵和阴离子表面活性剂十二烷基磺酸钠制备了有机蒙脱土,并通过红外光谱分析和X-射线衍射分析对其进行了表征。结果表明,有机插层剂已进入蒙脱土的层间,蒙脱土的层间距由1.24 nm分别增加到2.14,2.20和2.51 nm。沉降实验结果表明,这种有机蒙脱土在有机介质中表现出很好的分散性。     

表面活性剂和硅烷偶联剂有机复合改性蒙脱土的制备及性能表征

为增加蒙脱土与有机物的相容性,采用十六烷基三甲基溴化铵(CTAB)与硅烷偶联剂(KH-560)对蒙脱土进行了有机复合改性。X-射线衍射和红外光谱的结果表明,CTAB已插入蒙脱土片层,平均层间距离从1.54 nm增大到3.98 nm和2.08 nm,而KH-560未插入蒙脱土片层,只是覆盖在蒙脱土表面,未改变蒙脱土的插层结构;分散性实验表明,表面活性剂和硅烷偶联剂有机复合改性的蒙脱土在苯乙烯、液体石蜡中的分散性好于其他改性蒙脱土;有机复合改性不仅增大了蒙脱土层间距,且改善了蒙脱土与聚氯乙烯的界面效果,提高了蒙脱土在聚氯乙烯基体中的分散均匀性,从而使聚氯乙烯/蒙脱土复合材料玻璃化转变温度的提高和力学性能的改善更明显。     

Efficient preparation of isotactic polypropylene/montmorillonite nanocomposites by in situ polymerization technique via a combined use of functional surfactant and metallocene catalysis

In order to promote efficiency of the preparation of isotactic polypropylene (i-PP)/montmorillonite (MMT) nanocomposites by in situ polymerization technique, a strategy was laid out to enhance both the intercalative selectivity and the catalyst activity of the in situ polymerization by a combined use of a functional surfactant for MMT modification and a metallocene catalyst system for isospecific propylene polymerization. Thus, (2-hydroxylethyl) hexadecyl diethylammonium iodine was involved in the ion-exchanged organic modification of MMT, leading to an implantation of catalyst-anchoring reactive sites (hydroxyl, OH) in the interlayer galleries of MMT (OMMT). By treating the OH-intercalated OMMT successively with excessive methylaluminoxane (MAO) and rac-Me₂Si(2-Me-4-Ph-Ind)₂ZrCl₂, the metallocene catalyst typical for i-PP polymerization was stabilized inside the interlayer galleries with a catalytically benign environment. The MMT-borne catalyst, upon further activation by MAO, released fairly high activities for propylene polymerization. The effective intercalative polymerization ensured an efficient preparation of i-PP/MMT nanocomposite. A series of i-PP/MMT nanocomposites containing completely disordered MMT at a loading range of 1.0-6.7 wt% (TGA measurement residue at 600 °C) were obtained in high yields.