聚[丙烯酸甲酯-甲基丙烯酸2-(二甲氨基)乙酯]/环氧树脂IPN力学性能的研究

用同步法合成聚[丙烯酸甲酯-甲基丙烯酸2-(二甲氨基)乙酯]/环氧树脂(P(MA-DMA)/EP)互穿聚合物网络(IPN),对其力学性能进行了研究,结果表明,该体系IPN由于两网络间接枝导致相客性比较好,动态力学谱仅出现一个转变温度,当P(MA-DMA)/EP=20/80时,力学性能显示正协同效应,对环氧树脂的增韧效果最佳,不同组成比的IPNT_g实-T_g计与(d_实-d_计)差值成正比。     

STUDY ON SEGMENTED POLYURETHANE WITH MIXED SOFT SEGMENTS OF POLYCHLOROMETHYL METHYL SILOXANE AND POLYTETRAMETHYLENE OXIDE

Two series of polyurethanes based on mixed polychloromethyl methyl siloxane and poly-tetramethylene oxide in different weight fractions were synthesized. The phase separation ofsamples was studied using DSC and dynamic mechanical property analysis. The results showedthat the introduction of chloromethyl group into polysiloxane increased its polarity and henceimproved the miscibilities with polytetramethylene oxide and polyurethane hard segment.Particularly, in the case of N-methyldiethanolamine extended materials, the surface and tensileproperties of these samples can be adjusted by various ratios of two soft segments.     

Asymmetric addition of methyl nitroacetate to crotonaldehyde catalyzed by chiral amines

The asymmetric Michael addition of methyl nitroacetate to crotonaldehyde catalyzed by chiral amines was carried out. The maximum chemical yield of diastereomeric products amounted to 95 %. The best asymmetric induction (42 % e.e.) was achieved in the case of catalysis by (S)-prolinol. The diastereomeric mixture was converted to a mixture of stereoisomeric 3-methyl-2-methoxycarbonylpyrrolidines. Absolute configurations of (2S,3S)-and (2R,3S)-isomers formed in excess were determined using GLC by comparison with authentic samples of racemic and optically pure forms of 3-methylproline.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1591–1595, September, 1993.     

大孔-介孔氮掺杂二氧化钛的制备及其光催化性能测试

以嵌段共聚物为模板剂,甲酰胺为氮源,结合溶胶凝胶法制备了具有可见光活性的大孔-介孔氮掺杂二氧化钛(N-TiO2)材料.通过X射线衍射、低温N2吸附-脱附、扫描电镜、紫外-可见吸收光谱等手段,考察了嵌段共聚物对样品微结构和可见光活性的影响.结果表明,样品主要以锐钛矿相和板钛矿相混合形式存在;改变嵌段共聚物的浓度,可以制得晶粒粒径9～12 nm,孔径10～14 nm,禁带宽度2.98～2.76 eV的大孔-介孔N-TiO2,且随着模板剂加入量的增加,大孔孔径增大,孔壁增厚.对甲基橙溶液的室内自然光降解实验表明,大孔-介孔N-TiO2具有良好的光催化活性,随着嵌段共聚物加入量的增加,样品对甲基橙的降解时间缩短,降解率提高.     

Monomode Microwave‐Assisted Atom Transfer Radical Polymerization

Summary: The first monomode microwave‐assisted atom transfer radical polymerization (ATRP) is reported. The ATRP of methyl methacrylate was successfully performed with microwave heating, which was well controlled and provided almost the same results as experiments with conventional heating, demonstrating the absence of any “microwave effect” in ATRP (in contrast to several literature reports). Furthermore, we found that the main advantage of the microwave‐assisted reactions over conventional reactions, i.e., a significant increase of reaction rates, only had its limited application in ATRP, even in very slow ATRP systems with high targeted molecular weights.

Comparison of the kinetic plots of the ATRP of MMA ([MMA]₀/[EBIB]₀/[CuCl]₀/[NHPMI]₀ = 200:1:1:3, MMA/DMF = 1:1 v/v) carried out at 90 °C in DMF with microwave (▴) and conventional heating (•), respectively.     

Catalytic Upgrading of Biomass‐Derived Methyl Ketones to Liquid Transportation Fuel Precursors by an Organocatalytic Approach

A highly efficient water‐tolerant, solid‐base catalyst for the self‐condensation of biomass‐derived methyl ketones to jet‐diesel fuel precursors was developed by grafting site‐isolated secondary amines on silica‐alumina supports. It is shown that apart from the nature and density of amine groups and the spatial separation of the acidic and basic sites, the acidity of the support material plays a critical role in defining the catalytic activity. It is also found that a combination of weakly acidic silanol/aluminol with secondary amine groups can mimic proline catalysts and are more effective in catalyzing the selective dimerization reaction than the combination of amines with organic acids. In situ FTIR measurements demonstrate that acidic groups activate methyl ketones through their carbonyl groups leading to a favorable C? C bond formation step involving an enamine intermediate. DFT analysis of the reaction pathway confirms that C? C bond formation is the rate‐limiting step.     

酯交换法合成丙烯酸氯乙醇酯

丙烯酸卤代烷酯是重要的精细化工原料和中间体,一般的合成方法是直接酯化法。已有文献报道采用酯交换工艺以丙烯酸甲酯为原料制备丙烯酸高碳烷酯和丙烯酸二甲氨基烷酯[1-4]。Nolan等人曾报道了氮杂环卡宾作为催化剂通过酯交换反应合成甲基丙烯酸卤代烷酯[5,6],但是其催化剂制备     

Quantification of fatty acids as methyl esters and phospholipids in cheese samples after separation of triacylglycerides and phospholipids

Determination of the individual fatty acid composition of neutral- and phospholipids as well as the phospholipid content of dairy food and other foodstuffs are important tasks in life sciences. For these purposes, a method was developed for the separation of lipids (standards of triolein and diacylphosphatidylcholines as well as three cheese samples) by solid-phase extraction using a self-packed column filled with partly deactivated silica. Non-halogenated solvents were used for the elution of the lipid classes. Cyclohexane/ethyl acetate (1:1, v/v) served for the elution of neutral lipids, while polar lipids were eluted with three solvents (ethyl acetate/methanol, methanol, and methanol/water) into one fraction. The separated lipid fractions were transesterified and the individual fatty acids were quantified by using gas chromatography coupled to electron ionization mass spectrometry (GC/EI-MS) in the selected ion monitoring (SIM) mode. The recovery rate for standard phosphatidylcholines was ∼90% and cross-contamination from neutral lipids was negligible. The method was applied to cheese samples. Quantitative amounts of individual fatty acids in the phospholipid fraction were <0.002-0.29% of total lipids from camembert, <0.002-0.12% of total lipids from mozzarella, and <0.002-0.18% of total lipids in a goat cream cheese. Differences in the fatty acid pattern of neutral and polar lipids were detected. The quantity of the fatty acids determined in the phospholipid fraction was divided by the factor 0.7 in order to convert the fatty acid content into the phospholipid content of the cheese samples. This factor is based on the contribution of 16:0 to dipalmitoylphosphatidylcholine (DPPC). The resulting DPPC equivalents (DPPC_eq) were found to be representative for the average contribution of fatty acids to all classes of phospholipids in dairy products. Using this approach, the phospholipid content of lipids from mozzarella, camembert, and goat cream cheese was 0.60%, 1.42% and 0.79%, respectively.     

三维全息原子场作用矢量用于HEPT类抗艾滋病药物的QSAR研究

采用本实验室新近提出的三维全息原子场作用矢量表征34个1-[(2-羟乙氧)甲基]-6-苯硫基胸腺嘧啶(HEPT)类抗艾滋病药物结构并与其活性建立定量构效关系模型. 采用逐步回归对变量进行筛选后, 运用多元线性回归(multiple linear regression, MLR)建模的复相关系数(R2cum)、交互校验的复相关系数(Q2cum)和模型的标准偏差(SD)分别为R2cum=0.928、Q2cum=0.883与SD=0.43, 均优于Hancsh报道的值(R2cum=0.911、Q2cum=0.863与SD=0.45). 模型具有良好的稳定性和预测能力, 表明三维全息原子场作用矢量能较好表征该类分子结构信息, 值得进一步推广应用.     

Molybdosphoric Acid Mixed with Titania Used as a Catalyst to Synthesize Diphenyl Carbonate via Transesterification of Dimethyl Carbonate and Phenol

The 12-molybdosphoric acid mixed with titania (MPA-TiO2) was found to be a novel and efficient catalyst for the synthesis of diphenyl carbonate (DPC) via transesterification of dimethyl carbonate (DMC) and phenol. The X-ray diffraction (XRD) and infrared (IR) techniques were employed to characterize the prepared catalysts. The effect of the weight ratio of the 12-molybdosphoric acid to titania on the transesterification was investigated. A 13.1% yield of DPC and an 11.6% yield of methyl phenyl carbonate (MPC) were obtained over MPA-TiO2 with the weight ratio of MPA to TiO2 as 5:1.