以对甲苯磺酸为主催化剂合成三酚基乙烷的研究

为了提高标题化合物THPE的产率、简化操作过程,以苯酚和乙酰丙酮为原料,选用对甲苯磺酸和3-巯基丙酸作催化剂,合成了标题化合物;采用红外光谱分析、1HNMR和液相色谱对标题化合物的结构和纯度进行了表征。通过单因素试验,考察了原料配比、主催化剂用量、助催化剂用量、反应温度和反应时间对产率的影响,得出标题化合物的最佳合成工艺为:n(苯酚)∶n(乙酰丙酮)=9∶1;m(对甲苯磺酸)∶m(乙酰丙酮)=1∶1;m(3-巯基丙酸)∶m(乙酰丙酮)=1∶7;反应温度55℃;反应时间24 h;THPE粗产品产率稳定在78%以上。同时对其纯化处理进行了研究,1次CH2Cl2和4次乙醇/水提纯后产品的纯度达到了99.86%。

双(三氯硅基)乙烷的醇解研究

以双(三氯硅基)乙烷为原料,通过醇解反应制备了双(三乙氧基硅基)乙烷。研究了溶剂种类、进料方式、醇解温度、反应时间、原料配比、氮气流速对双(三乙氧基硅基)乙烷收率的影响。较佳工艺为:双(三氯硅基)乙烷与乙醇的量之比1∶6.5,正己烷作溶剂,原料于40~50℃滴入乙醇,同时以50 m L/min的流速通入氮气吹除HCl气体,此条件下产物的收率可达95%。

三唑类抗真菌药物中间体(2R,3S)-2-(2,4-二氟苯基)-3-甲基-[(1H-1,2,4-三氮唑-1-基)甲基]环氧乙烷合成方法

综述并分析了三唑类抗真菌药物中间体(2R,3S)-2-(2,4-二氟苯基)-3-甲基-[(1H-1,2,4-三氮唑-1-基)甲基]环氧乙烷的合成方法,对工业化生产的技术方法提出了建议。

1,1,1-三氟-2-氯乙烷的应用进展

1,1,1-三氟-2-氯乙烷可开发多种氟碳化合物,合成各类三氟乙基下游产品,还在含氟农药、医药等领域有着广泛的应用价值。

Synthesis and characterization of hybrid organic-inorganic materials based on EA-MAn-APTES and silica

Poly (EA-MAn-APTES)/silica hybrid materials were successfully prepared fromEthyl acrylate (EA), maleic anhydride (MAn) and tetraethoxysilane (TEOS) in the presence of acoupling agent 3-aminopropyltriethoxysilane (APTES),by free-radical solution polymerization and insitu sol-gel process. The mass fraction of TEOS varied from 0 to 25%. The hybrid materials werecharacterized by the methods of FT-IR spectra, solvent extraction, scanning electron microscope (SEM), transmission electron microscope (TEM), differential scanning calorimetry (DSC) andthermogravimetric analysis (TGA) measuring apparatus to get their structures, gel contents,morphologies, particle sizes and thermal performances. The results show that the covalent bonds arebetween organic and inorganic phases, gel contents in the hybrid materials are much higher, theSiO_2 phase is well dispersed in the polymer matrix, silicon dioxide exist at nanoscale in thecomposites and have excellent thermal stability.

导电硅橡胶的制备与性能优化设计

通过硅氢加成反应合成了一种新型1,2-双(三甲氧基硅基)乙烷。以此为交联剂,与107硅橡胶、填料、乙炔炭黑、催化剂配混,制得双组分脱醇型室温硫化导电硅橡胶。通过正交实验设计法对硅橡胶的导电性及综合性能进行了研究。结果表明,较佳的配方是:在100份107硅橡胶中,填加75份乙炔炭黑,5.0份气相法白炭黑,2.0份新型交联剂,2.0份结构化控制剂。

Syntheses and Crystal Structures of 4,4′Diformyl-diphenoxyethane and 4,4′4′′-Triformyl-triphenoxytriethylamine

Two title compounds, 4,4?diformyl-diphenoxyethane (compound 1, C16H14O4) and 4,4?4创-triformyl-triphenoxytriethylamine (compound 2, C27H27NO6), were synthesized by condensation of 4-hydroxybenzaldehyde with 1,2-dichloroethane and tris(2-chloroethyl)amine, respectively in dimethyl formamide in the presence of anhydrous potassium carbonate. The crystal data are: monoclinic, P21/c, a = 7.571(2), b = 12.608(3), c = 7.357(2) ? b = 105.823(6)? V = 675.7(2) 3, Mr = 270.3, Z = 2, Dc = 1.328 g/cm3, F(000) = 284, m(MoKa) = 0.096 mm-1, R = 0.0537 and wR = 0.2189 for compound 1; and monoclinic, P21/n, a = 11.7162(6), b = 9.0042(6), c = 22.908(2) ? b = 99.505(1)? V = 2383.5(3) ?, Mr = 461.50, Z = 4, Dc = 1.286 g/cm3, F(000)= 976, m(MoKa) = 0.091 mm-1, R = 0.0464 and wR = 0.1462 for compound 2. The molecule of compound 1 (dialdehyde) is located at the crystallographic inversion center nearby the midpoint of C(8)C(8A) single bond. The three chains in the molecule of compound 2 (trialdehyde) are of non-crystallographic pseudo-C3 symmetry, and each of them is quite planar.

Study and Characterization of Organically Modified Silica-Zirconia Anti-Graffiti Coatings Obtained by Sol-Gel

In this work, it is presented the synthesis and characterization of transparent and colorless organic-inorganic hybrid anti-graffiti protective materials obtained by sol-gel method. This type of materials is based on MTES （methyltriethoxysilane）, TPOZ （tetrapropoxide of zirconium） and PDMS （polydimethylsiloxane）. The synthesis has been carried out at 25, 35 and 45 ℃ in order to evaluate the role of temperature in the structure, microstructure and anti-graffiti behavior as well. The incorporation of zirconium within the organic modified silica network, of sols after being gelled and dried, is evident by a shoulder which increased with temperature situated at 950 cml （Si-O-Zr bonds）, and it is homogenously dispersed inside the matrix avoiding the formation of large ZrO2 precipitates. As the temperature increases, the hydrolysis and condensation reactions occur in more extension and thus, the obtained sols are more cross-linked and present more Si-O-Zr linkages. The promising anti-graffiti beha＇4ior of the protectNe hybrids was qualitatively determined being the spot removal higher than 90%.

Selective removal of heavy metal ions from aqueous solutions with surface functionalized silica nanoparticles by different functional groups

The industrial silica fume pretreated by nitric acid at 80 °C was re-used in this work. Then, the obtained silica nanoparticles were surface functionalized by silane coupling agents, such as(3-Mercaptopropyl) triethoxysilane(MPTES) and(3-Amincpropyl) trithoxysilane(APTES). Some further modifications were studied by chloroaceetyl choride and 1,8-Diaminoaphalene for amino modified silica. The surface functionalized silica nanoparticles were characterized by Fourier transform infrared(FI-IR) and X-ray photoelectron spectroscopy(XPS). The prepared adsorbent of surface functionalized silica nanoparticles with differential function groups were investigated in the selective adsorption about Pb2+, Cu2+, Hg2+, Cd2+ and Zn2+ions in aqueous solutions. The results show that the(3-Mercaptopropyl) triethoxysilane functionalized silica nanoparticles(SiO2-MPTES) play an important role in the selective adsorption of Cu2+ and Hg2+, the(3-Amincpropyl) trithoxysilane(APTES) functionalized silica nanoparticles(SiO2-APTES) exhibited maximum removal efficiency towards Pb2+ and Hg2+, the 1,8-Diaminoaphalene functionalized silica nanoparticles was excellent for removal of Hg2+ at room temperature, respectively.

Microwave radiation one-pot synthesis of chloropropyl-functionalized mesoporous MCM-41

Chloropropyl-functionalized mesoporous MCM-41（MCM-41-（CH2）3Cl） was synthesized in alkaline medium by the microwave radiation one-pot method, using cetyltrimethy-lammoniumbromide （CTAB） as novel template, tetraethoxysilane （TEOS） as silica source, and chloropropyltriethoxysilane （C1PTES） as the coupling agent. The microstructure of MCM-41-（CH2）3Cl was characterized by the means of X-ray diffraction （XRD）, nitrogen absorption-desorption, Fourier transform infrared spectroscopy （FT-IR）, scanning electron microscopy （SEM）, and transmission electron microscopy （TEM）. The results show that a successful synthesis of MCM-41-（CH2）3Cl with well structure is obtained. The optimal microwave power is 120 W and the best microwave time is 50 rain. The dosage of chloropropyltriethoxysilane on the structure of chloropropyl-functionalzed MCM-41 was also investigated. It is found that the chloropropyltriethoxysilane volume between 0.8 mL and 1.6 mL is favorable for the formation of highly ordered MCM-41-（CH2）3Cl mesostructure.

Effect of Aminoaromatic Acids as Additives on the Activity and Selectivity of the Platinum-catalyzed Hydrosilylation of Alkenes

A series of aromatic acids has been tested as additives for the platinum-catalyzed hydrosilylation of styrene with triethoxysilane. Both excellent conversion of styrene and selectivity in favor of the ,β-adduct were achieved using aminobenzoic acids as additive. Moreover, the use of 4-aminobenzoic acid led to significantly superior enhancement in both catalytic activity and selectivity among the tested aminobenzoic acids. Indeed, 100% conversion of styrene and 98.4% selectivity in favor of the β-adduct were obtained. Additionally, hydrosilylations of various alkenes with a variety of platinum catalysts have also been tested, and in each case the conversion of substrate and the selectivity of the β-adduct were promoted by using 4-aminobenzoic acid as additive.

Measurement and correlation of solubility of trimethylolethane in different pure solvents and binary mixtures

The solubilities of trimethylolethane in butanol,methyl acetate,ethyl acetate as well as in mixed solvents of(methanol+ethyl acetate) and(ethanol+ethyl acetate) were measured with the gravimetric method in the temperature range from 283.15 K to 318.15 K under atmosphere pressure.The experiment results showed that the solubility of trimethylolethane increased with the temperature,or along with the concentration of methanol or ethanol in the solvents of(methanol+ethyl acetate) and(ethanol + ethyl acetate).In addition,the experiment values were correlated by the van't Hoff equation,Modi fied Apelblat Equation,λh Equation,CNIBS/R-K equation and Jouyban–Acree Model.The Modi fied Apelblat Equation provided the best fitting results of the solubility data of TME in the pure solvents while the CNIBS/R-K model showed the best estimation of the solubility in the binary solvent mixtures.Furthermore,the density functional theory(DFT) calculations showed that solubility in different solvents related to the strength of the interaction between the trimethylolethane and the solvent molecules.Finally,the standard molar enthalpy and molar entropy of trimethylolethane during the dissolving process was also calculated by Modi fied Apelblat equation in this work.

Nano-indentation profiles of intrinsic hardness and modulus of films based on silsesquioxane modified with titanium tetrabutoxide

This study is to analyze the influence of the modifier, 5～25 wt % titanium tetrabutoxide (TBO), on the hardness and elastic modulus of the films based on SSO deriving from hydrolytic condensation of (3-glycidoxypropyl)trimethoxysilane (GPMS) and vinyltrimethoxysilane (VMS), by the continuous stiffness measurement (CSM) technique of an instrumented-indentation testing (IIT) device. Films were synthesized by adding the stoichiometric amount of ethylenediamine (EDA) and benzoyl proxide (BPO) to SSO solutions in ethanol, dip-coating over glass substrates, and curing using an appropriate thermal cycle. Intrinsic values of hardness and elastic modulus were determined with the average values in “plateau region” from “four-layer” explanation. And the brittle index of the modified coating systems was analyzed.

Isobaric Vapor-Liquid Equilibrium for Methyldichlorosi-lane+Methylvinyldichlorosilane+Toluene and Constituent Binary Systems

Vapor-liquid equilibrium (VLE) for a ternary system of methyldichlorosilane + methylvinyldichlorosi-lane + toluene and constituent binary systems were measured at 101.3kPa using a new type of magnetical pump-ebulliometer. The equilibrium compositions of the vapor phase of binary systems were calculated indirectly from the total pressure-temperature-liquid composition (pTx). The experimental data were correlated with the Wilson and NRTL(non-random two liquid) equations. The parameters of the Wilson model were employed to predict the ternary VLE data. The calculated boiling points were in good agreement with the experimental ones.

304不锈钢表面复合硅烷膜的制备及其耐蚀性能

本文利用1,2双(三乙氧基硅基)乙烷(BTSE)和1H,1H,2H,2H全氟癸基三氯硅烷(FDTS)两种硅烷自组装修饰304不锈钢表面,制备BTSE、FDTS硅烷膜和BTSE FDTS复合硅烷膜。通过原子力显微镜(AFM)、X线能谱分析(EDS)和静态接触角(WCA)对样品进行表征。实验表明:与单层BTSE和FDTS硅烷膜相比,BTSE FDTS复合硅烷膜厚度更大(平均厚度为30 nm),F元素分布均匀且更致密,疏水性更强,静态接触角达到120°。极化曲线和加速腐蚀试验表明BTSE FDTS复合硅烷膜的抗腐蚀性能优于单层硅烷膜和未修饰的不锈钢。与未修饰的不锈钢相比,复合硅烷膜的缓蚀效率达到84.2%,腐蚀损失率减少72.8%。

Surface modification of magnesium hydroxide by γ-aminopropyltriethoxysilane

Magnesium hydroxide(MH),which is commonly used as a halogen-free flame retardant filler in composite materials,was modified by silanization reaction with γ-aminopropyltriethoxysilane (γ-APS) in aqueous solution at different pH values (pH range from 8.0 to 12.0). The surface properties of grafted γ-APS on MH surface as a function of solution pH value were studied using elemental analysis,Fourier transform infrared spectroscopy and zeta potential measurement. The results show that hydrolysis and condensation of γ-APS are activated in alkaline solution and lead to multilayer adsorption of γ-APS molecules on the surface of MH. The type of adsorption orientation of γ-APS on MH surface is a function of coverage density that is altered by changing solution pH value. At low coverage density (e.g. 55 nm-2),γ-APS molecules are preferentially adsorbed to the surface with the silicon moiety towards the surface,and increasing coverage density (e.g. 90 nm-2) leads to parallel orientation. At an even higher coverage density (e.g. 115 nm-2),γ-APS molecules bond to the surface with the amino moiety towards the surface.

Self-assembled Carbon Nanotube/Silicone Composite Films and Their Electrical Properties for Electrical Device

Novel composites were synthesized using AEPTES （3-（2-aminoethylamino）propyltriethoxysilane）, which behaves as an excellent dispersant for MWCNTs （multiwall carbon nanotubes） in polymer film matrices. The thickness of the synthesized nanocomposite films ranged from 50 to 70 lam, having well-dispersed MWCNTs. Increasing the AEPTES concentration from 0.0196 to 0.0300 M, increased the amine content and the dispersion of MWCNTs. The film synthesized at 0.0300 M AETPES exhibited the greatest degree of dispersion among the three samples, which is consistent with a self-assembled silane group interacting with the MWCNT surface.

Residues of organochlorine pesticides in intertidal flat surface sediments from coastal zone of Jiangsu Province, China

Sixteen surface sediment samples were collected and analysed to evaluate the residues of organochlorine pesticides （OCPs） from intertidal fiat in Jiangsu Province. Overall, 22 OCPs were detected with total concentrations of OCPs ranging widely from 0.96 to 12.14 ng/g （dry wt）. Total hexachlorocyclohexane （HCH） and total dichlorodiphenyltrichloroethane （DDT） levels varied from 〈0.01 to 0.67 ng/g and from 0.23 to 4.85 ng/g, respectively. DDTs were the predominant compounds. The dominance of β-HCH indicated a history of HCH pollution. According to the ratios of （p,p＇-DDD＋p,p＇-DDE）/p,p＇DDT and o,p＇-DDT/p,p＇- DDT, new input of DDTs did not occur in most sites, and the main sources were historical usage of technical DDTs. OCPs such as dieldrin, endrin, p,p＇-DDD, and p,p＇-DDT exceeded the effects range low, showing adverse biological effects that would occasionally occur at some sites of the study area.

Highly Efficient Asymmetric Transcyanation of Acetyltrimethylsilane with Acetone Cyanohydrin Catalyzed by (R)-Oxynitrilase from Prunus Japonica Seed Meal

Highly efficient asymmetric transcyanation of acetyltrimethylsilane with acetone cyanohydrin in an aqueous/organic biphasic system catalyzed with （R）-oxynitrilase from defatted Prunus Japonica seed meal for the preparation of optically active （R）-2-trimethylsilyl-2-hydroxyl-propionitrile was successfully carried out for the first time. For better understanding of the reaction, various influential variables were examined with respect to the initial reaction rate, the substrate conversion and the product enantiomeric excess （e.e.）. Diisopropyl ether was found to be the best organic phase for this reaction among all the organic solvents tested. The optimal concentrations of Prunus Japonica seed meal powder, acetyltrimethylsilane and acetone cyanohydrin, volume ratio of aqueous phase to organic phase, buffer pH value and the reaction temperature were 34.5g·L^-1 and 14mmol· L^-1, 28mmol· L^-1, 13% （by volume）, 5.0 and 30℃, respectively, while the initial reaction rate, the substrate conversion and the product enantiomeric excess were 1.34 mmol·L^-1·h^-1, 99.0% and 99.0%, respectively. The comparative study demonstrated that silicon atom in substrate showed great effect on the reaction and acetyltrimethylsilane was a much better substrate for （R）-hydroxynitrile lyase from Prunus Japonica seed than its carbon analogue 3,3-dimethyl-2-butanone.