Variation of anions in layered double hydroxides: Effects on dispersion and fire properties

Layered double hydroxides (LDHs) are interesting materials for nanocomposite formation because one can vary the identity of the metals, the anions and the stoichiometry to see the effect of these on the ability of the nano-material to disperse in a polymer and to see what effect dispersion has on the properties of the polymer. In this study, the anions 2-ethylhexyl sulfate (SEHS), bis(2-ethylhexyl) phosphate (HDEHP) and dodecyl benzenesulfonate (SDBS) have been utilized as the charge balancing anions to synthesize organo-LDHs. Nanocomposites of poly(methyl methacrylate) (PMMA) and polystyrene (PS) with organo-LDHs were prepared both by melt blending and bulk polymerization. X-ray diffraction and transmission electron microscopy were used to characterize the morphology of the nanocomposites while the thermal stability and fire properties of nanocomposites were studied by thermogravimetric analysis and cone calorimetry; the mechanical properties are also investigated. In general, it is easier to disperse these organo-LDHs in PMMA than in PS, but the sulfate cannot be dispersed at the nanometer level in either material. The addition of these organo-LDHs does not affect the mechanical properties. The best fire properties are obtained with the sulfonate LDH, SDBS; the reduction in the peak heat release rate is almost 50% for both polymers.     

Synthesis and characterization of expandable graphite-poly(methyl methacrylate) composite particles and their application to flame retardation of rigid polyurethane foams

The expandable graphite (EG) is well proved to be a good intumescent flame retardant for rigid polyurethane foam (RPUF), however, as it is pulverized into fine particles (pEG) for the purpose of improving the mechanical properties of the foam composite, the flame-retardant properties of pEG-filled RPUF (pEG/RPUF) are deteriorated. To improve both the mechanical properties and flame-retardant performance of pEG/RPUF composite, the pEG particles were encapsulated with a layer of polymer, poly(methyl methacrylate) (PMMA). The Fourier transform infrared spectroscopy (FTIR) examination, thermogravimetric analysis (TGA) and scanning electron microscopy (SEM) observation well demonstrated that the pEG-PMMA particles were successfully synthesized via emulsion polymerization, with 22.09 wt% PMMA. In contrast to the pEG, the addition of 10 wt% of pEG-PMMA particles into RPUF led to a considerable increase of the compressive strength and modulus and flame retardancy (limiting oxygen index, horizontal and vertical burning rates). The improvement of mechanical properties and flame-retardant behavior of pEG-PMMA particles filled RPUF was attributed to the desirable dispersion of pEG in PU matrix without destroying the integrality of the RPUF cell system, the good interfacial adhesion between PMMA and RPUF, and sealing the fine EG particles without losing oxidant, hence, to increase their expanded volume as exposed to fire.     

Evaluation of the Efficiency of the Macrolactonization Using MNBA in the Synthesis of Erythromycin A Aglycon

Various intermediates for the synthesis of erythronolide A, an aglycon of erythromycin A, are prepared from the corresponding seco‐acids using 2‐methyl‐6‐nitrobenzoic anhydride (MNBA) in the presence of 4‐(dimethylamino)pyridine (DMAP) with or without triethylamine. The efficiency of the MNBA lactonization is assessed by studying this method and comparing the results with those of the other established macrocyclization protocols. It has been finally concluded that (i) the conformationally appropriate substrate for the monomeric cyclization gave the desired lactone in excellent yield under mild reaction conditions in the presence of MNBA and DMAP, (ii) the highly‐strained substrate for the cyclization also afforded the monomeric lactone in relatively good yield at 100°C in toluene, and (iii) the seco‐acid having stable linear conformation, which preferred dimerizing more than forming the monomeric lactone, provided the corresponding diolide in high yield with the constant ratio of the monomer to dimeric lactone (approximately 1/5). © 2009 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 9: 305–320; 2009: Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.200900017     

一种具有抗肿瘤活性胆酸衍生物的合成新方法

以胆酸为原料, 使之与甲醇反应, 得到胆酸甲酯(2). 2采用PCC(氯铬酸吡啶)氧化得到脱氢胆酸甲酯(3), 3在CoCl2存在的条件下通过NaBH4的化学选择性还原得到7α-羟基-3,12-二氧代胆酸甲酯(4). 对4的抗肿瘤活性试验表明该化合物对Sk-Hep-1(肝癌)和H-292(肺癌)细胞株具有中等程度的细胞毒性.     

苯氨基甲酸甲酯分解催化剂Bi-Zn复合氧化物的制备及其催化性能

采用共沉淀法制备了一系列Bi-Zn复合氧化物催化剂并将其用于催化苯氨基甲酸甲酯(MPC)分解制备苯基异氰酸酯(PI).用热重、X射线衍射和傅里叶变换红外光谱考察了Bi/Zn摩尔比和焙烧温度对催化剂物相结构和表面性质的影响.结果表明,Zn的加入使Bi_2O_3由α晶相转变为活性更高的β晶相,500℃焙烧时Bi-Zn前驱体分解较为完全,析出Bi_2O_3粒子的同时伴生较多Bi_(7.65)Zn_(0.35)O_(11.83)晶相.在Bi/Zn摩尔比为2/1,焙烧温度为500℃条件下制得的催化剂活性最高,此时MPC转化率为86.O%,PI选择性为91.7%,优于单独使用Bi_2O_3时的催化性能.     

Synthesis of dimethyl ether from methane mediated by HBr (Special column of methane transformation, Article)

Dimethyl ether (DME) was synthesized from methane through a two-step process, in which CH₃Br was prepared from the oxidative bromination reaction of methane in the presence of HBr and oxygen over a Rh-SiO₂ catalyst and then, in the second step, CH₃Br was hydrolyzed to DME over a silica supported metal chloride catalyst. 12 mol%ZnCl₂/SiO₂ catalyst was found to be the most active, but it deactivated because of Cl⁻ losing.     

层离型PMMA/镁铁双氢氧化物纳米复合材料的热降解研究

通过原位聚合方法制备了以非水溶性聚合物(聚甲基丙烯酸甲酯,PMMA)为基体,与MgFe双氢氧化物(LDH)具有良好相容性的层离型纳米复合材料.采用小角、广角X射线衍射(XRD)及透射电镜(TEM)对纳米复合材料的微观结构进行了分析,通过热重分析(TG)和玻璃化转变研究了纳米复合材料在空气和氮气氛围下的热降解过程.实验结果表明,MgFe-LDH的引入显著提高了聚合物基体的热降解温度和玻璃化转变温度,纳米复合材料的热稳定性显著提高.其中含量1.6 wt%的层离型纳米复合材料在失重50%时的热降解温度比纯样提高约69℃.并且整个纳米复合体系的相容性良好,含量8.0 wt%的样品,其可见光透过率仍可达90%以上.     

通过原子转移自由基聚合合成可光交联的聚苯乙烯接枝共聚物

聚苯乙烯(PS)在氯化锌(ZnCl_2)做催化剂下,通过氯甲基甲基醚氯甲基化反应,合成了氯甲基化聚苯乙烯(CMPS).在氯化亚铜/联二吡啶(CuCl/bpy)催化下,以CMPS为大分子引发剂引发甲基丙烯酸甲酯(MMA)、甲基丙烯酸酯化查尔酮(MSPK)进行原子转移自由基聚合,成功合成了侧链含有查尔酮结构的光敏聚苯乙烯接枝共聚物(PSMM),所得聚合物结构经过红外光谱(FT-IR)、核磁共振氢谱(~1H NMR)得到确认,通过热重分析(TG)、示差扫描量热法(DSC)测试了该聚合物的热学性能.结果表明,该接枝共聚物具有较好的热学性能及良好的光敏性.     

Synthesis of novel biodegradable poly(ethylene glycol) analogue:Water-soluble aliphatic polyester with pendant oligo(ethylene glycol) chains

A novel poly(ethylene glycol)(PEG) analogue composed of aliphatic polyester backbone and pendant oligo(ethylene glycol) short chains is reported.The PEG analogue is a copolymer synthesized by ring-opening alternating copolymerization of succinic anhydride with 2-((2-(2-metho xyethoxy)ethoxy)methyl)oxirane.The structure of the copolymer was confirmed by ~1H NMR spectrum.The effects of the monomer feed ratio on the copolymerization were studied and the polymerization mechanism was given.The PEG analogue di...     

(R)-2-甲基半胱氨酸盐酸盐的合成方法改进

以L-半胱氨酸甲酯盐酸盐为起始原料,经4步反应合成了(R)-2-甲基半胱氨酸盐酸盐.在关键中间体(2R, 4R)-2-叔丁基-3-甲酰基-4-甲基-1,3-噻唑烷-4-甲酸甲酯(4)的合成中,采用Self-regeneration of stereocenters原理,用六甲基二硅胺钠取代文献方法中的二异丙基胺基锂,4的收率由文献的56%提高至90%.化合物的结构经1H NMR和MS表征.