含三乙基硅基FI催化剂的合成及其在制备超高分子量聚乙烯中的应用

以卤代苯酚为原料,在咪唑和4-二甲氨基吡啶存在下,与三乙基氯硅烷反应,得到酚氧邻位为三乙基硅基取代的取代苯酚,随后与多聚甲醛反应,得到取代水杨醛,与伯胺通过醛胺缩合,得到苯氧亚胺配体,最后与金属络合,得到两种含三乙基硅基的苯氧亚胺锆催化剂,用于催化乙烯聚合制备超高分子量聚乙烯。在聚合温度为70℃,乙烯压力1.0 MPa,n(Al)/n(Zr)=7000条件下,以甲苯为溶剂,催化剂j的催化活性可达8.45 kg PE/(mmol·Zr·h),所得聚乙烯的黏均分子量介于100×104~800×104 g/mol,其熔点139℃,结晶度49.7%。

三乙基硅基乙炔的合成

研究了三乙基氯硅烷制备三乙基硅基乙炔的方法。实验中详细考察了格式反应的影响因素,通过条件实验对格式工艺进行了优化。反应总收率达72.1%。

1-(2-三甲基硅氧乙基)-5-巯基四氮唑的合成研究

以乙醇胺为起始原料,经三甲基氯硅烷保护制得2-(三甲基硅氧基)乙胺,再经与二硫化碳反应,再与溴乙烷缩合得到N-(2-三甲基硅氧乙基)二硫代氨基甲酸乙酯、然后再与叠氮化钠成环反应合成了1-(2-三甲基硅氧乙基)-5-巯基四氮唑。用三甲基氯硅烷作为乙醇胺的羟基保护试剂,保护和脱保护具有反应条件温和、收率高等优点,反应总收率高达85%以上。

萘基桥联有机-无机杂化介孔材料的合成及其光学性质(英文)

以短链阳离子三聚表面活性剂[C10H21N+(CH3)2(CH2)2N+(CH3)(C10H21)(CH2)2N+(CH3)2C10H21]·3Br-为结构导向剂,通过2,7-二(3-三乙氧硅基氨丙酯基)萘(NIS)和四乙氧基硅烷(TEOS)共缩聚,制备了有序的萘基桥联的杂化周期性介孔有机硅(PMOs).样品通过X射线衍射(XRD)、高分辨透射电镜(HRTEM)、氮气吸附-脱附、差示扫描量热/热重分析(DSC/TGA)表征.结果表明,当NIS占NIS和TEOS总量40%(摩尔分数)时,可以形成具有结晶态孔壁的有序介孔杂化材料.当NIS含量低于或高于40%时,分别形成无定形孔壁的有序介孔杂化材料和无孔杂化材料.随着孔壁中萘基基团的增加,由于有机基团之间π-π堆积作用增强,杂化介孔材料显示良好的热稳定性.由于在二氧化硅骨架中嵌入荧光萘基基团,杂化有机-无机有序介孔材料显示了激基缔合物的光学行为.随萘基基团含量的增加,杂化材料的紫外吸收峰发生蓝移,形成H聚集体;由于聚集引起的荧光淬灭,杂化材料的荧光量子产率明显降低.

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.

L-胱氨酸功能化的Au@SiO_2-DPTS比色检测Pb^(2+)

以具有核-壳结构的Au@Si O2纳米颗粒为基底,用二乙基磷酰乙基三乙氧基硅烷(DPTS)和L-胱氨酸(L-Cystine)对其进行功能化修饰制备得二乙基磷酰乙基三乙氧基硅烷和L-胱氨酸功能化纳米金粒子(L-Cys-Au@Si O2-DPTS),利用羧酸根及磷酸根与铅离子形成金属螯合物后,引起纳米粒子的聚集,导致溶液由酒红色变为蓝色,这种颜色的转变可通过肉眼直接识别,从而建立起一种简单,快速且的可用于现场实时检测Pb2+的可视化比色检测的方法。通过优化p H、底物浓度和反应时间等条件后,相较于Ni2+,Co2+,Mn2+等9种金属离子,L-Cys-Au@Si O2-DPTS对Pb2+显示出了极高的选择性。在最优实验条件下,检测Pb2+时,浓度在10-5~10-4mol/L范围内呈现出良好的线性关系(R2=0.9983),最低检测限为3.43×10-8mol/L。

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%.

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.

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.

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.

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.

Synthesis, characterization of triphenyltin grafted on SBA-15mesoporous silica and its catalytic performance for the synthesis of 4-methylacetophenone

The production of Ph3Sn–O–SBA-15(Ph3Sn SBA)was achieved by heating triphenyltin chloride and SBA-15in N-methylpyrrolidone at 190°C for 5 h using triethylamine as a catalyst.The composition,structure,and surface physical and chemical properties of Ph3Sn SBA were characterized using inductively coupled plasma-atomic emission spectroscopy(ICP-AES),13C,119Sn and29Si solid-state nuclear magnetic resonance(NMR)spectroscopy in situ pyridine infrared spectroscopy(Py-IR),N2adsorption–desorption isotherms,X-ray diffraction(XRD)and transmission electron microscopy(TEM).The results of ICP-AES and organic elemental analysis showed that the grafting yield of Sn was 17%(by mass)for Ph3Sn SBA.The elemental analysis and solid-state NMR results for Ph3Sn SBA were consistent with grafting of triphenyltin on SBA-15.The N2adsorption–desorption,XRD and TEM analyses showed that Ph3Sn SBA retained an ordered hexagonal mesoporous structure,resulting in decreases in the surface area,pore size and mesopore volume,and an increase in acidity as compared with SBA-15.The Hammett acidity function(H0)value and the number of acid sites for Ph3Sn SBA,obtained by the Hammett methods,were 2.77–3.30 and 2.07 mmol·g-1,respectively.The Friedel–Crafts acylation of toluene and acetic anhydride over Ph3Sn SBA was investigated.The yield of methylacetophenone(MAP)and the selectivity for 4-methylacetophenone(PMAP)were 79.56%and 97.12%,respectively,when the conditions were n(toluene):n(anhydride)=2.0:1.0 with 6%(by mass)catalyst,and heating under reflux for 5 h.The PMAP selectivity still reached 93.11%when Ph3Sn SBA was used for the fifth time under the same reaction conditions.