正丁胺对晶态层状苯乙烯基膦酸-磷酸氢锆的插层研究

合成了晶态层状有机-无机多功能材料苯乙烯基膦酸-磷酸氢锆(α-ZPPVPA),并研究了正丁胺(BA)对α-ZPPVPA的插层性能。用元素分析、XRD、IR、TG、SEM和TEM等分析方法对α-ZPPVPA及其插层化合物α-ZPPVPA-BA进行了结构表征和形貌分析。结果表明,正丁胺成功地插入了α-ZPPVPA层板之间,层间距为2.41 nm,正丁胺的插入使α-ZPPVPA的层间距(1.66 nm)增大了0.75 nm,插入的正丁胺在α-ZPPVPA中呈双分子层排列,且苯乙烯基侧链不饱和双键的存在不影响α-ZPPVPA与正丁胺的插层反应。     

混合金属氧化物柱撑α-磷酸锆的研究

制备、表征了混合铝/铬金属氧化物柱撑α-磷酸锆(Al/Cr-ZrP),并对胶体化使用有机胺的种类、柱化液金属离子浓度以及金属离子用量等因素进行了研究。研究表明以乙醇胺为胶体化有机胺比使用正丙胺为胶体化有机胺所得到的产物的层间距更大;采用较低金属离子浓度、较高金属离子用量有利于Al/Cr-ZrP的合成。在Al/Cr比为1、以正丙胺为胶体化有机胺、金属离子浓度为0.067mol·L^-1、金属离子用量为6.67CEC的条件下,制备出了混合金属氧化物柱撑α-磷酸锆,其层间距可达3.60nm,     

正丁胺对苯膦酸铜的插层反应研究

分别采用溶液搅拌和超声的方法,研究了有机正丁胺分子对苯膦酸铜的插层反应.对插层复合物进行了红外光谱(IR)、X射线粉末衍射(XRD)和热重分析等测试及结构分析.结果表明,有机正丁胺的插入使得苯膦酸铜的层间距增大.     

层状(脯氨酸-N-甲基膦酸-磷酸氢)锆的合成及插层性能研究

以高结晶度制备了层状(脯氨酸-N-甲基膦酸-磷酸氢)锆(α-ZPMPP)晶体(层间距为1.52nm),并研究了其常温下对正丁胺的插层性能,用元素分析、IR、XRD和TG-DSC热分析对α-ZPMPP及其插层复合物进行了表征.结果表明,层状α-ZPMPP具有形成超分子主-客体化合物的插层性能,正丁胺客体分子在主体底物中形成单分子层,并插入α-ZPMPP中,使层间距增大0.45nm,插入的正丁胺可在150～250℃被脱除.     

丹参酮与胺类化合物的反应研究

研究了隐丹参酮与氨、甲胺、乙胺等有机胺的作用。发现丹参酮二氢呋喃环部分在氨及NaOH的作用下发生亲核开环,且亲核加成反应与开环反应协同进行。与甲胺、乙胺等有机胺作用则分别生成丹参酮的咪唑环及恶唑环衍生物。探讨了可能的反应历程。     

基于液晶取向变化检测有机胺化合物的方法

采用旋涂法在玻璃基底表面制备4-三乙氧基硅基丁腈有机膜.有机膜表面采用丝绒布进行摩擦和5％乙酸水溶液改性处理后成为特异敏感膜.将此敏感膜的载玻片面对面贴合后,在其间组装液晶E7分子膜,表征液晶分子排列状态;采用挥发法在敏感膜表面组装液晶膜,制备成了检测目标物的复合材料.采用此种材料对甲胺、乙胺和二乙胺等有机胺化合物及实验室常见干扰气体进行检测,发现只有有机胺化合物会对材料的液晶分子排列状态产生影响,导致液晶膜的亮度发生改变,从而实现对目标物的特异检测.对有机胺化合物检测过程中,其响应速率为V甲胺＜V乙胺＜V二乙胺,恢复速率为:V乙胺＜V乙胺＜V甲胺;刘乙胺的检出限为0.46 mg/m3.本方法具有较高的检测灵敏度,抗干扰能力较强且操作简单,可发展为现场检测有机胺化合物的新技术.     

直接置换插层法0.85 nm水合高岭石的制备

以高岭石/尿素插层复合物作为中间相,利用简单的直接置换插层法制备了d001=0.85 nm的水合高岭石。利用X射线衍射、红外光谱、扫描电镜表征处理前后高岭石结构与形貌的变化。结果表明:尿素插层后的高岭石层间距从d001=0.72 nm增大到d001=1.08 nm,经不同温度酸洗或水洗后,插层复合物转变成层间有水分子的水合高岭石(d001=0.85 nm),且高岭石晶粒厚度明显从约25 nm减小到约10 nm。在高温条件下形成的水合高岭石含量最高,90℃水洗时d001=0.85 nm水合高岭石的转化率接近70%,这种水合高岭石具有进一步的置换插层能力,是一种制备其他高岭石插层复合物很好的前驱体。与乙二醇形成d001=1.10nm乙二醇/高岭石插层复合物,其置换率达到100%。     

长链烷胺及手性钛的螯合物Ti[(OC2H4)3N][OCH(CH3)2]在层状V2O5中的插层行为

用一种简便快速方法合成了一系列长链有机胺插层V₂O₅化合物. 用粉末X射线衍射(XRD)、红外光谱(FT-IR)、漫反射紫外-可见光谱(DR UV-VIS)等手段对插层产品的结构进行了表征. 除了正十六胺插层V₂O₅产品外, 其它长链烷胺插层V₂O₅产品的层间距d₀₀₁与长链烷胺碳数n之间具有良好的线性关系: d₀₀₁＝0.160n_C＋0.731 nm. 正十六胺与V₂O₅反应后生成两个插层相, 一个相的层间距d₀₀₁为4.01 nm, 另一相的d₀₀₁为3.20 nm. 此外, 研究了手性钛的螯合物Ti[(OC₂H₄)₃N][OCH(CH₃)₂] (记为TEAIP)在V₂O₅层间的插层行为, 得到相应的插层产品.     

新环氧树脂纳米复合材料的合成和结构研究

以具有层状硅酸盐结构的累托石(REC)为主体,以烷基季铵盐为改性剂合成了有机累托石(OREC),以有机累托石和环氧树脂复合,制备出纳米复合材料。累托石含量在0.8wt.% 时,纳米复合材料具有最佳力学和热学性能,冲击强度增加到65.6 kJm-2,断裂伸长率从4.7 %增加到20.2 %,玻璃化转变温度提高到 197.9 ℃。用X-小角衍射法、透射电镜和红外吸收光谱研究了材料的微观结构,XRD 衍射图显示,未经处理REC 的层间距d001 = 2. 2 nm,经有机改性后,累托石片层间距扩大到2.8 nm,与环氧树脂复合后,其层间距扩大到4.2 nm 左右,FT-IR图显示,有机累托石中出现十六胺的特征吸收峰,TEM照片显示该复合材料是一种纳米复合材料。     

高抗冲聚苯乙烯/蒙脱土复合材料的阻燃性研究

用经十六烷基三甲基溴化铵有机化改性的蒙脱土 (OMMT)与高抗冲聚苯乙烯 (HIPS)通过熔融插层法制备了HIPS OMMT复合材料 ,用X ray衍射技术对材料结构进行了表征 ,发现钠基蒙脱土 (Na+ MMT)和有机蒙脱土的层间距分别为 1 5 1nm和 2 18nm ,HIPS OMMT(5phr)复合材料中蒙脱土的层间距因聚合物大分子的插入扩大为 3 4 4nm ;而HIPS与Na+ MMT形成的复合材料的层间距与Na+ MMT的层间距相比却没有变化 ,表明未有机化处理土没有形成插层结构 .锥形量热仪的研究结果表明HIPS OMMT复合材料的热释放速率、质量损失速率以及生烟速率等燃烧特性参数均显著降低 ,具有较明显的阻燃性和抑烟性 ,而HIPS Na+ MMT非插层型复合材料只有在Na+ MMT很高填充量下 (>2 0phr)才有一定阻燃效果 .比较了铵盐对HIPS阻燃性的影响 ,结果表明铵盐自身的阻燃作用很小 ,主要是插层复合结构起阻燃作用 .     

四苯基卟啉在改性磷酸锆层间的插入及荧光增强

近年来,出于节约一次性能源的考虑,人们已经加大对太阳能等天然资源的利用,致力于模拟天然光合作用的研究[1￣3],而光合作用中的捕光复合物又称为光子天线。光子天线中往往存在一种或几种猝灭剂,猝灭剂吸收光子后产生激发态的能量可以在不同分子或者同一分子的不同生色团之间转移,转移出能量的一方为能量给体,另一方为能量受体。     

Intercalation of non-aromatic heterocyclic amines into layered zirconium glycine-<Emphasis Type="Italic">N,N</Emphasis>-dimethylphosphonate

New materials were prepared by intercalation reactions between layered zirconium glycine-N,N-dimethylphosphonate (ZGDMP) and non-aromatic heterocyclic amines: piperazine, piperidine, and morpholine. X-ray powder diffraction patterns showed that the entrance of piperazine, piperidine, and morpholine caused an interlayer expansion of 0.40 nm, 0.66 nm, and 0.67 nm, respectively. The infrared spectra were in agreement with an acid-base reaction, involving layered acid host COOH of ZGDMP and basic center atoms of guest molecules. Thermogravimetric curves revealed thermal stability of the intercalation compounds and content of the inserted amine molecules. These results indicate that non-aromatic heterocyclic amines were intercalated into the galleries of host ZGDMP.     

Intercalation of poly(oxyethylene) alkyl ether into a layered silicate kanemite

Poly(oxyethylene) alkyl ether (CnEOm) is intercalated into the interlayer space of a layered silicate kanemite by using layered hexadecyltrimethylammonium (C16TMA) intercalated kanemite (C16TMA-kanemite) as the intermediate. C16TMA-kanemite was treated with an aqueous solution of C16EO10, and the intercalation of C16EO10 was confirmed by the slight increase in the basal spacing (from 2.92 to 3.34 nm) with the increase in the carbon content, yielding C16EO10-C16TMA-kanemite. The product was dispersed again in a C16EO10 aqueous solution, and then 1.0 M HCl was added to the suspension to remove C16TMA ions completely. The basal spacing was further increased (from 3.34 to 5.52 nm) and the content of nitrogen was virtually zero, indicating further intercalation of C16EO10 molecules and complete elimination of C16TMA ions simultaneously. Though C16EO10 molecules are not directly intercalated into kanemite, the mutual interactions among C16TMA ions, C16EO10 molecules, and the interlayer silicate surfaces effectively induce the intercalation of C16EO10. C16EO10-kanemite shows a reversible adsorption of n-decane and water owing to the hydrophobicity and hydrophilicity of C16EO10, respectively, in the interlayer space. Layered CnEO10-kanemites (n = 12 and 18) were also synthesized in a manner similar to layered C16EO10-kanemite.     

不同链长的聚醚铵阳离子协同插层对蒙脱土性能的影响

为了制备高性能的聚合物/蒙脱土纳米复合材料, 必须对蒙脱土(MMT)进行有机改性来改善蒙脱土表面的疏水性、提高蒙脱土与聚合物之间的相容性, 同时也需要尽可能地增大蒙脱土的层间距. 为此, 提出了一种采用不同链长的聚醚铵阳离子协同插层MMT 的新方法, 即采用D2000(或T5000)聚醚铵盐与D400 聚醚铵盐协同插层MMT, 并采用X射线衍射分析(XRD)和热重分析(TGA)研究了协同插层对改性MMT 的层间距、有机含量以及耐热性的影响. 另外, 也研究了插层过程中的搅拌方式和D400 聚醚铵盐多次插层对改性MMT 的层间距、有机含量等的影响. 研究结果表明,采用长链聚醚铵阳离子协同插层更有利于提高D400 聚醚铵盐改性MMT 的层间距和有机含量; T5000 协同插层MMT中总的有机含量(64.06%)进一步增加, 这可能是因为T5000 的支链在MMT 层间形成的笼型结构既提供了更大的空隙,又起到了屏蔽作用, 同时也得到了较大的层间距(6.86 nm).     

十六烷基三甲基溴化铵插层氧化石墨结构的分子模拟

利用分子模拟方法研究了十六烷基三甲基溴化铵(C16TAB)分子数对C16TAB/GO插层复合物的结构变化,探讨了C16TAB在GO层间的排列方式,并通过实验数据进行验证。模拟结果表明,优化后GO结构模型的层间距为0.849 nm;C16TAB/GO插层复合物的层间距随着C16TAB分子数的增加呈5个阶梯状逐渐增大,层间距分别为1.56、1.98、2.33、2.76和3.40 nm,插层饱和时C16TAB分子达到28个。实验结果显示,随着C16TAB分子数的增加,C16TAB/GO插层复合物的层间距逐渐增大,插层饱和时为3.40 nm,实验结果与模拟结果能够很好地吻合。C16TAB在GO层间可能的排列方式为1~5层平躺排列或单层平躺、单层倾斜和单层直立,从能量和结构的角度探明了C16TAB在GO层间的最优排列为1~5层平躺排列。     

十六烷基三甲基溴化铵插层氧化石墨结构的分子模拟

利用分子模拟方法研究了十六烷基三甲基溴化铵(C₁₆TAB)分子数对C₁₆TAB/GO插层复合物的结构变化,探讨了C₁₆TAB在GO层间的排列方式,并通过实验数据进行验证.模拟结果表明,优化后GO结构模型的层间距为0.849 nm;C₁₆TAB/GO插层复合物的层间距随着C₁₆TAB分子数的增加呈5个阶梯状逐渐增大,层间距分别为1.56、1.98、2.33、2.76和3.40 nm,插层饱和时C₁₆TAB分子达到28个.实验结果显示,随着C₁₆TAB分子数的增加,C₁₆TAB/GO插层复合物的层间距逐渐增大,插层饱和时为3.40 nm,实验结果与模拟结果能够很好地吻合.C₁₆TAB在GO层间可能的排列方式为1~5层平躺排列或单层平躺、单层倾斜和单层直立,从能量和结构的角度探明了C₁₆TAB在GO层间的最优排列为1~5层平躺排列.     

Biopolymer-layered polysilicate micro/nanocomposite based on chitosan intercalated in magadiite

On the basis of their high adsorption and cation exchange capacity, swelling potential and low toxicity, layered sodium silicate magadiite (Na–magadiite) is an attractive solid for intercalation of polymers. This study envisages the intercalation of cationic biopolymer chitosan (Chit) in Na–magadiite to prepare a Chit/magadiite micro/nanocomposite. Characterisation of starting-magadiite, pure chitosan and Chit/magadiite were investigated using powder X-ray diffraction analysis (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy and thermal analysis. XRD confirmed that the chitosan had been intercalated into the interlayer space of magadiite by increasing the basal spacing, d₀₀₁ from 15.6 Å to 21.45 Å. The presence of characteristic bands of biopolymer and layered silicate in Chit/magadiite were confirmed by FTIR analysis. The thermal stability of micro/nanocomposite was evaluated by thermogravimetry analysis. The results suggested the formation of electrostatic interactions by protonated amine groups with the negatively charged magadiite surface as well as intercalation in the form of a predominant monolayer arrangement of chitosan chains in layered silicate magadiite.     

Synthesis and UV absorption properties of 2,3-dihydroxynaphthalene-6-sulfonate anion-intercalated Zn-Al layered double hydroxides

An organic UV absorbent has been intercalated into a layered double hydroxide (LDH) host by ion exchange of a Zn-Al-LDH-nitrate precursor with a solution of 2,3-dihydroxynaphthalene-6-sulfonic acid (DNSA) sodium salt in water. After intercalation of the UV absorbent, the powder X-ray diffraction (XRD) pattern shows that the interlayer distance in the LDHs increases from 0.90 to 1.59 nm. The possible structure is that the interlayer DNSA anions arrange in a monolayer and in a perpendicular orientation toward the hydroxide layers. Infrared spectra and TG-DTA curves reveal the presence of a complex system of supramolecular host-guest interactions between layers. The thermal stability of the intercalated UV absorbent was investigated by TG-DTA and it was found that this material is more stable than the original organic UV absorbent at high temperature, showing that the thermostability is markedly enhanced after intercalation into the LDH host. The UV absorbent-intercalated LDHs exhibit excellent UV photostability in polypropylene composites.     

A study on the intercalation and exfoliation of illite

Illite particles were exfoliated from the illite-organics intercalation precursor in the ultrasound process. Four intercalating agents (glycerol, hydrazine hydrate, dimethyl sulfoxide, and urea) were selected to study the intercalation reaction for purified illite, thermal activated illite, and acidified illite and to prepare different illite-organics intercalation complexes. The resulting intercalation complexes and exfoliated illite were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), the zeta potential test, the particle size test and thermogravimetry analysis (TG). XRD results showed that the thermal activation and subsequent acidification treatment to exchange K⁺ in the interlayer of illite with H⁺ is a necessary condition for organic intercalation. FTIR and TG analysis confirmed the intercalation of four intercalating agents into the interlayer of illite. During the high-temperature ultrasonic treatment, the organic molecules were deintercalated from the interlayers of illite-organics intercalation complexes, leading to the separation of the illite layers. The d₀₀₁ diffraction of illite in XRD patterns became broad and weak after ultrasonic treatment; this indicated the random orientation of illite platelets. Particle size analysis showed the exfoliated illite (IUE) from the illite-urea intercalation complex possessed the smaller particle diameter. SEM and TEM observation showed the particle size of IUE is 0.5–4 μm with a layer thickness of approximately 200–300 nm. Moreover, the exfoliation of illite layers exposed more internal layers with negative charge, leading to the decrease of zeta potential.     

Preparation of 5-benzotriazolyl-4-hydroxy-3-sec-butylbenzenesulfonate anion-intercalated layered double hydroxide and its photostabilizing effect on polypropylene

An organic UV absorber has been intercalated into a layered double hydroxide (LDH) host by ion-exchange method using ZnAl-NO₃-LDH as a precursor with an aqueous solution of the sodium salt of 5-benzotriazolyl-4-hydroxy-3-sec-butylbenzenesulfonic acid (BZO). After intercalation of the UV absorber, the interlayer distance in the LDHs increases from 0.89 to 2.32 nm. Infrared spectra and thermogravimetry and differential thermal analysis (TG-DTA) curves reveal the presence of a complex system of supramolecular host-guest interactions. The thermostability of BZO is markedly enhanced by intercalation in the LDH host. ZnAl-BZO-LDHs/polypropylene composite materials exhibit excellent UV photostability.