高岭石/APTES插层复合物的表征及其脱嵌反应动力学

以高岭石/甲醇(K/M)复合物为前驱体,利用置换法制备出了高岭石/γ-氨丙基三乙氧基硅烷插层复合物(K/APTES),并应用XRD、FTIR、TEM、TG-DSC分析等表征手段对复合物进行了分析。结果表明:APTES分子的氨基与前驱体K/M的四面体硅氧烷基、嫁接在铝氧八面体表面上的甲氧基均发生键合作用形成氢键,APTES分子为两层倾斜排列于高岭石层间,倾角大小与温度有关。插层剂APTES破坏了高岭石层间的氢键,加剧了高岭石自身结构中硅氧四面体片层与铝氧八面体片层之间存在的错位,使得K/APTES插层复合物的部分片层卷曲变形。还针对复合物的插层剂APTES的脱嵌反应,采用Satava积分法和AcharBrindley-Sharp-Wendworth微分法相结合的动力学方法计算得到了完整的动力学三因子:活化能E=197.8 k J·mol-1,指前因子的对数lg(A/s-1)=14.60,最概然机理函数为:f(α)=[-ln(1-α)]-1,G(α)=α+(1-α)ln(1-α)。     

高岭石/APTES插层复合物的表征及其脱嵌反应动力学

以高岭石/甲醇(K/M)复合物为前驱体,利用置换法制备出了高岭石/γ-氨丙基三乙氧基硅烷插层复合物(K/APTES),并应用 XRD、FTIR、TEM、TG-DSC分析等表征手段对复合物进行了分析.结果表明:APTES分子的氨基与前驱体K/M的四面体硅氧烷基、嫁接在铝氧八面体表面上的甲氧基均发生键合作用形成氢键,APTES分子为两层倾斜排列于高岭石层间,倾角大小与温度有关.插层剂APTES破坏了高岭石层间的氢键,加剧了高岭石自身结构中硅氧四面体片层与铝氧八面体片层之间存在的错位,使得K/APTES插层复合物的部分片层卷曲变形.还针对复合物的插层剂APTES的脱嵌反应,采用Satava积分法和Achar-Brindley-Sharp-Wendworth微分法相结合的动力学方法计算得到了完整的动力学三因子:活化能E=197.8 kJ·mol^-1,指前因子的对数lg(A/s^-1)=14.60,最概然机理函数为:f(α)=[-ln(1-α)]^-1,G(α)=α+(1-α)ln(1-α).     

高岭土/二甲亚砜插层复合物脱嵌反应热动力学

采用TG和XRD研究了高岭土/二甲亚砜插层复合物的脱嵌反应过程, 提出了一种新的动力学计算方法. 首先用迭代的等转化率法求得反应的活化能Ea, 然后用Malek法拟合得到最可能的机理函数G(α)和f(α), 最后用多升温速率-等温法求得了指前因子A. 研究结果表明, 高岭土/二甲亚砜的插层物脱嵌反应的活化能Ea=86.65 kJ/mol, 指前因子A位于1.6050×108~3.6151×108 s-1之间. 其反应机理为n级的化学反应, 机理函数是G(α)=[1-(1-α)1-n]/(1-n), f(α)=(1-α)n. n值和升温速率有一定的关系, 当升温速率较大(30 ℃/min)或较小(5 ℃/min)时, n=1.5, 当升温速率为7~25 ℃/min时, n=1.6.     

高岭石-硬脂酸插层复合物的制备及结构模型的提出

以张家口高岭土为原料,通过直接插层与取代相结合的方法制备高岭石-硬脂酸插层复合物。利用X射线粉末衍射、红外光谱、热重及透射电子显微镜对制备产物进行表征。结果表明:硬脂酸插入到高岭石层间,高岭石层间距d001值由0.72 nm增加到4.05~4.37 nm,插层率达到86.9%;反应时间和溶液p H值会对高岭石-硬脂酸插层复合物的层间距及插层率产生影响;甲氧基嫁接在高岭石表面,与硬脂酸分子同时存在于高岭石层间。高岭石经甲醇改性后脱羟基温度明显降低,高岭石羟基活性提高;高岭石-硬脂酸插层复合物的稳定温度在160℃以下。经过硬脂酸插层改性后的高岭石片层,从边缘开始出现卷曲现象,并且部分长条状片层形成类似埃洛石相的纳米卷;对硬脂酸插层高岭石的作用机理进行分析,结合结构计算,提出高岭石-硬脂酸插层复合物的结构模型,该模型可以解释高岭石-硬脂酸插层复合物在不同条件制备产物层间距变化的原因。     

高岭石插层效率评价

用基于X射线衍射分析(XRD)的插层率、基于热重分析(TGA)的热失重率和基于红外光谱分析(FTIR)的3 600 cm^-1谱带与3 700 cm^-1谱带强度比值对高岭石/二甲基亚砜(DMSO)插层复合物和高岭石/N-甲基甲酰胺(NMF)插层复合物的插层效率进行了综合评价。结果表明,当插层反应进行到1、6和25 d,高岭石/DMSO的插层率分别为5%、52%和89%;而高岭石/NMF的插层率则分别为93%、94%和95%。与此同时,高岭石/DMSO的热失重率分别为1.06%、8.06%和17.46%;而高岭石/NMF的失重率分别为6%、6.5%和14.2%。在红外光谱图中,高岭石/DMSO复合物的3 600与3 700 cm^-1带强度比分别为1.03,1.141和1.628,而高岭石/NMF复合物分别为1.403,1.433和1.612。3种评价方法显示很好的一致性,相对而言,在插层作用的初期,XRD方法比较灵敏,而在插层作用的后期,TGA和FTIR方法则显得更为灵敏和有效。     

高岭石-硬脂酸插层复合物的制备及结构模型的提出

以张家口高岭土为原料,通过直接插层与取代相结合的方法制备高岭石-硬脂酸插层复合物.利用 X射线粉末衍射、红外光谱、热重及透射电子显微镜对制备产物进行表征.结果表明:硬脂酸插入到高岭石层间,高岭石层间距d₀₀₁值由0.72 nm增加到4.05~4.37 nm,插层率达到86.9%;反应时间和溶液pH值会对高岭石-硬脂酸插层复合物的层间距及插层率产生影响;甲氧基嫁接在高岭石表面,与硬脂酸分子同时存在于高岭石层间.高岭石经甲醇改性后脱羟基温度明显降低,高岭石羟基活性提高;高岭石-硬脂酸插层复合物的稳定温度在160 ℃以下.经过硬脂酸插层改性后的高岭石片层,从边缘开始出现卷曲现象,并且部分长条状片层形成类似埃洛石相的纳米卷;对硬脂酸插层高岭石的作用机理进行分析,结合结构计算,提出高岭石-硬脂酸插层复合物的结构模型,该模型可以解释高岭石-硬脂酸插层复合物在不同条件制备产物层间距变化的原因.     

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%。     

聚氧化乙烯/高岭石聚合物电解质的制备与表征

通过尿素对高岭石的插层及随后的超声脱除处理,制备了一种片层剥离的高岭石粉体,并将这种剥离高岭石与聚氧化乙烯/高氯酸锂(PEO/LiClO_4)体系复合,制备出PEO/高岭石复合物.采用X射线衍射仪、红外光谱仪、扫描电子显微镜、透射电子显微镜、扫描量热仪、电化学工作站和万能材料试验机进行结构表征和性能测试.结果表明,尿素在高岭石层间的插层和脱除引起了高岭石片层的剥离,片层厚度小于50 nm.剥离高岭石在PEO/LiClO_4体系中与PEO形成了强烈的氢键作用,促进了PEO结晶度的降低,进而提高复合物的离子电导率.含有20 wt%剥离高岭石填料的PEO/高岭石复合物的离子电导率达到6.0×10~(-5) S/cm,与未复合的PEO/LiClO_4相比,提高了一个数量级.复合物制备过程中的烘干温度对PEO的结晶度会产生一定的影响,95°C下的烘干处理能得到结晶度较低,离子电导率较高的复合物.此外,剥离高岭石的添加显著提高了聚合物的杨氏模量和拉伸强度,与未复合的PEO/LiClO_4相比,杨氏模量和拉伸强度最大提高了256%和121%.     

Y_2O_3前驱体热分解过程及动力学研究

用热重-差热分析法对Y_2O_3前驱体Y_2(CO_3)_3和Y_2(C_2O_4)_3水合物热分解过程及动力学进行分析,通过Kissinger法、 Ozawa法和Coast-Redfern法等对实验数据进行处理,得出Y_2(C_2O_4)_3水合物的热分解分四步进行,前两步为脱水过程,后两步为分解过程,四步反应对应的活化能E_c分别为64.24, 59.48, 146.20和112.37 kJ·mol~(-1);指前因子A_c分别为:4.09×10~8, 3.83×10~5, 6.86×10~(10)和6.18×10~5。每一步的机制函数分别是:1-(1-α)~(1/2)=kt, 1-(1-α)~(1/3)=kt,[(1-α)~(-2)-1]/2=kt和[-ln(1-α)]~(1/3)=kt。而Y_2(CO_3)_3在空气中热分解只有两步,第一步脱3个H_2O和1个CO_2分子,第二步脱2个CO_2分子生成Y_2O_3,两步对应的活化能E_c分别为88.29和116. 53 kJ·mol~(-1),指前因子A_c分别为1.5×10~(13)和9.4×10~7。它们的机制函数分别为(1-α)~(-1)-1=kt和[1-(1-α)~(1/3)]~2=kt。前驱体Y_2(CO_3)_3水合物相对来说比Y_2(C_2O_4)_3水合物更易分解生成Y_2O_3,两种前驱体的热分解都是最后一步为控速步骤。     

电荷转移盐(C_3H_5N_2H)_3[PMo_(12)O_(40)]的合成与热分解及光致变色反应动力学

用磷钼酸与咪唑合成了一种新的杂多酸-有机电荷转移盐(C3H5N2H)3[PMo12O40]。通过元素分析、红外光谱、固体漫反射光谱、电子自旋共振及热分析等测试技术对其进行了表征,用单扫描法(Achar法和Coats-Redfern法)对合成化合物的TG分析结果进行了非等温热分解动力学研究。推断结果表明,合成化合物的第1步热分解为球对称的三维扩散机理(n=2),其动力学方程为dα/dt=1.58×108[1-(1-α)1/3]-1(1-α)2/3exp(-40931.0/T),求得分解反应的表观活化能E=340.30kJ/mol,指前因子A=1.05×108s-1。标题化合物对紫外光具有光致变色性质,用固体漫反射光谱研究了其光致变色反应动力学。结果显示,其光致变色反应表现为一级或准一级动力学,速率常数k=9.80×10-5s-1。     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.     

Synthesis of N-substituted carbazolones from α-iodo enaminones via Pd(0)-catalyzed intramolecular coupling under microwave irradiation

A variety of N-aryl and N-alkyl carbazolones were conveniently achieved in good to high yields via Pd₂(dba)₃-mediated intramolecular coupling of N-substituted α-iodo enaminones under microwave irradiation. The Pd(0)-catalyzed cyclization was found to proceed favorably with the more electron-deficient phenyl ring during the reactions involving unsymmetrical N,N-diaryl α-iodo enaminones. This unique property enables the construction of carbazolone skeleton containing nitro substituted benzenoid ring.     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles by intramolecular nitrilimine cycloaddition

Both substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles have been synthesized by the 3+2 intramolecular dipolar cycloaddition of nitrilimines to alkynes. This cyclization has been extended to more versatile 3-bromo derivatives by the use of alkynylbromides as dipolarophiles.