Selective hydrogenation of maleic anhydride to gamma-butyrolactone in supercritical carbon dioxide

The reaction rates of the hydrogenation of maleic anhydride (MAH) and succinic anhydride (SAH) were significantly accelerated and the selectivity to gamma-butyrolactone (GBL) was enhanced largely when the reaction mixture was pressurized by a non-reactant of CO2. Above 99% selectivity to GBL was achieved in 14 MPa CO2, the superior selectivity in scCO(2) was attributed to that MAH and/or SAH could be extracted to CO2 phase and separated from H2O, the hydrolysis were thus minimized and so the selectivity to GBL was improved.

Carbon dioxide pressure induced heterogeneous and homogeneous Heck and Sonogashira coupling reactions using fluorinated palladium complex catalysts

The Heck reaction of iodobenzene and methyl acrylate was investigated with CO2-philic Pd complex catalysts having fluorous ponytails and the organic base triethylamine (Et3N) in the presence of CO2 under solventless conditions at 80 degrees C. The catalysts are not soluble in the organic phase in the absence Of CO2 and the reaction occurs in a solid-liquid biphasic system. When the organic liquid mixture is pressurized by CO2, CO2 is dissolved into the organic phase and this promotes the dissolution of the I'd complex catalysts. As a result, the Heck reaction occurs homogeneously in the organic phase, which enhances the rate of reaction. This positive effect Of CO2 pressurization competes with the negative effect that the reacting species are diluted by an increasing amount of CO2 molecules dissolved. Thus, the maximum conversion appears at a CO2 pressure of around 4 MPa under the present reaction conditions. The catalysts are separated in the solid granules by depressurization and are recyclable without loss of activity after washing with n-hexane and/or water.

Interaction Between Tripeptide Gly-Gly-His and Cu2+ Probed by Microcantilevers

Gly-Gly-His tripeptide modified microcantilever was developed by carbodiimide attachment of the Gly-Gly-His tripeptide onto a 3-mercaptopropionic acid(MPA) modified gold surface. The interaction of peptide with Cu2+ ion was studied. At a relative high concentration of Cu2+, the cantilever bent toward the gold side initially as the N atom of imidazole ring and carboxyl group in different peptide coordinate with Cu2+, which results in a tensile surface stress. And then the reversed deflection of microcantilever was observed, which implies that the peptide-Cu2+ complex are formed with conformation transition. In another case, i.e., at a relative low concentration Of Cu2+, only the process of conformation transition was observed due to the coordination mode can not be formed initially. The influences of pH and salt concentration of the test solution on the performance of the sensor were studied. The results show that the maximum deflection was obtained at pH 7 and the bonding Of Cu2+ to the Gly-Gly-His tripeptide was inhibited due to the formation Of CuClx2-x.

微悬臂梁检测三肽Gly-Gly-His与Cu~(2+)的相互作用过程

将三肽Gly-Gly-His(GGH)共价键合到MPA修饰的微悬臂梁表面,研究了肽与Cu2+的相互作用过程。研究发现,在Cu2+浓度较高时,Cu2+能快速与不同肽链上的羧基和咪唑环配位,并通过连锁反应诱导悬臂梁向镀金面偏转;而后肽链上的氮原子与Cu2+配位,同时构象发生变化,由直链转变成折叠状,进而增加链间的作用力使悬臂梁反向偏转;而Cu2+浓度低时不能实现连锁反应诱导悬臂梁表面快速的形成向内的拉力,直接通过构象变化推动悬臂梁反向偏转。考察了溶液pH值、Cl-浓度对GGH与Cu2+作用的影响,结果表明,在pH7.0的条件下GGH与Cu2+作用导致悬臂梁偏转最大。Cl-的存在会与Cu2+形成CuCl2x?x配合物不易与肽链结合。

高韧性异构聚酰亚胺树脂及其复合材料

采用MPMR合成技术得到了低黏度、高韧性、耐高温异构聚酰亚胺树脂,该树脂预浸液常温储存期大于两个月,亚胺化后纯树脂在320℃熔体黏度<300 Pa.s,树脂浇铸体的弯曲强度>100 MPa,弯曲模量>3.0 GPa,抗拉强度可达80 MPa,断裂伸长率可达6%,固化后T5d>500℃,其中PI-4复合材料在300℃的弯曲强度保持率达到76.5%。

Microstructure, thermal stability and mechanical properties of the novel (W1-xAlx)C-Co (x=0.2, 0.33, 0.4, 0.5) cemented carbide

Bulk novel cemented carbides (W1-xAlx)C-10.1 vol% Co (x = 0.2, 0.33, 0.4, 0.5) are prepared by mechanical alloying and hot-pressing sintering. Hot-pressing (HP) is used to fabricate the bulk bodies of the hard alloys. The novel cemented carbides have good mechanical properties compared with WC-Co. The density and operating cost of the novel material is much lower than a WC-Co system. The material is easy to process and the processing leads to nano-scaled, rounded, particles in the bulk material. The hardness of (W1-xAlx)C-10.1 vol% Co (x = 0.2, 0.33, 0.4, 0.5) hard material is 20.37, 21.16, 21.59 and 22.16 GPa, and the bending strength is 1257, 1238, 1211 and 1293 MPa, with the aluminum content varying from 20% to 50%. The relationship between the microstructure and the mechanical properties of the novel hard alloy is also discussed.

NOVEL COMPOSITES OF POLY(L-LACTIDE) AND SURFACE MODIFIED BIOACTIVE SiO2-CaO-P2O5 GEL NANOPARTICLES: MECHANICAL AND BIOLOGICAL PROPERTIES

Bioactive SiO2-CaO-P2O5 gel (BAG) nanoparticles with 40 nm in diameter were synthesized by the sol-gel route and further modified via the ring-opening polymerization of lactide on the surface of particles. Surface modified BAG (mBAG) was introduced in poly(L-lactide) (PLLA) matrix as bioactive filler. The dispersibility of mBAG in PLLA matrix was much higher than that of rough BAG particles. Tensile strength of the mBAG/PLLA composite could be increased to 61.2 MPa at 2 wt% filler content from 53.4 MPa for pure PLLA. The variation of moduli of the BAG/PLLA and mBAG/PLLA composites always showed an enhancement tendency with the increasing content of filler loading. The SEM photographs of the fracture surfaces showed that mBAG could be homogeneously dispersed in the PLLA matrix, and the corrugated deformation could absorb the rupture energy effectively during the breaking of materials. In vitro bioactivity tests showed that both BAG and mBAG particles could endow the composites with ability of the calcium sediment in SBF, but the surface modification of BAG particles could weaken this capability to some extent. Biocompatibility tests showed that both BAG and mBAG particles could facilitate the attachment and proliferation of the marrow cells on the surface of the composite.

Microstructures and mechanical properties of extruded Mg-8Gd-0.4Zr alloys containing Zn

Microstructures and mechanical properties of the Mg-8Gd-xZn-0.4Zr (x = 0, 1 and 3 wt.%) alloys in the as-cast, as-extruded and extruded-T5 conditions, have been investigated. The peak-aged Mg-8Gd-1Zn-0.4Zr alloy during isothermal ageing at 423 K acquires highest mechanical properties, with the highest ultimate tensile strength and yield tensile strength of 314 and 217 MPa, respectively. Addition of Zn has obvious effect on age hardening responses, especially for 1 wt.% Zn addition. It is due to a uniform distribution of beta' phase which can impede the movement of dislocations. However, addition of 3 wt.% Zn to the Mg-8Gd-0.4Zr alloy leads to a precipitation of Mg3Zn3Gd2 phase (W-phase). This phase is incoherent with interface of the matrix and becomes cores of the fracture in tensile test at room or elevated temperature.

镱对AZ91D镁合金显微组织和力学性能的影响

在Mg-9Al-1Zn合金的基础上添加不同质量分数的Yb,制备了4种合金。通过X射线衍射、金相显微镜、扫描电镜及能谱分析仪等手段分析了Yb的添加对AZ91D显微组织和力学性能的影响。结果表明:Yb的加入,显著改变了AZ91D合金的铸态组织,细化了β-Mg17Al12相,且β-Mg17Al12脆性相由连续网状分布逐渐变为离散状,同时晶界上出现了块状的Al11Yb3和点状Al6Mn4Yb化合物。当Yb含量为1.0%时,该合金具有最佳的综合力学性能,抗拉强度达到194 MPa,比AZ91D提高22%,伸长率和硬度也随着Yb含量的增加而提高。研究表明,重稀土元素Yb在镁合金中显示出与轻稀土更相近的作用效果。

Influence of Zn content on the microstructure and mechanical properties of extruded Mg-5Y-4Gd-0.4Zr alloy

Microstructures and mechanical properties of the Mg-5Y-4Gd-xZn-0.4Zr alloys have been investigated. These results show that the Mg-5Y-4Gd-0.5Zn-0.4Zr alloy in the peak-aged condition exhibits the highest tensile strength, and the values of the ultimate tensile strength and yield tensile strength are 370 and 300 MPa, respectively. It is suggested that addition of 0.5% Zn has a great effect on age hardening response. The long periodic stacking structure has been found in these Zn-containing alloys, and the volume fraction of this phase increases with increasing Zn addition. This phase plays an important role in improvement of the mechanical properties, especially for the elongations. The beta' phase precipitates during the ageing process are responsible for the improvement of the mechanical properties of the alloys in the peak-aged condition.

Effect of Zn concentration on the microstructures and mechanical properties of extruded Mg-7Y-4Gd-0.4Zr alloys

Microstructures and mechanical properties of the Mg-7Y-4Gd-xZn-0.4Zr (x = 0.5, 1.5, 3, and 5 wt.%) alloys in the as-cast, as-extruded, and peak-aged conditions have been investigated by using optical microscopy, scanning electron microscope, X-ray diffraction, and transmission electron microscopy. It is found that the peak-aged Mg-7Y-4Gd-1.5Zn-0.4Zr alloys have the highest strength after aging at 220 A degrees C. The highest ultimate tensile strength and yield tensile strength are 418 and 320 MPa, respectively. The addition of 1.5 wt.% Zn to the based alloys results in a greater aging effect and better mechanical properties at both room and elevated temperatures. The improved mechanical properties are mainly ascribed to both a fine beta' phase and a long periodic stacking-ordered structure, which coexist together in the peak-aged alloys.

Microstructures and properties of Mg-7Gd alloy containing Y

Mg-7 mass%Gd-x mass%Y (x = 0, 1, 3 and 5) alloys were prepared by casting method, and the microstructures, age hardening behavior and mechanical properties have been investigated. The results show that the addition of Y to the binary Mg-7Gd alloy could reduce the grain size of the as-cast alloys, and enhance the age hardening response and improve mechanical properties during the investigated temperature range. The Mg-7Gd-5Y alloy exhibits maximum ultimate tensile strength and yield strength at peak hardness, and the values are 258 and 167 MPa at room temperature, and 212 and 140 MPa at 250 degrees C, respectively, which is about 1.8 times as high as the Mg-7Gd binary alloy. When x is more than 3, the amount of Mg-5 (Gd,Y) phase is observed at the peak hardness of aged alloys. The significant improvement of the tensile strength at peak hardness is mainly attributed to the fine dispersion of the beta-Mg-5(Gd,Y) precipitate.

Microstructures and mechanical properties of Mg-8Gd-0.6Zr-xNd (x=0, 1, 2 and 3 mass%) alloys

Mg-8Gd-0.6Zr-xNd (x = 0, 1, 2 and 3 mass%) alloys were prepared by metal mould casting method, and the microstructures, age hardening responses and mechanical properties have been investigated. The microhardness of the as-cast alloys is increased with increasing Nd content. The age hardening behavior and mechanical properties are enhanced significantly by adding Nd element. The peak ageing hardness of the Mg-8Gd-0.6Zr-3Nd alloy is 103, it is about 1.3 times more than that of the Mg-8Gd-0.6Zr alloy. The aged Mg-8Gd-0.6Zr-3Nd alloy exhibits maximum ultimate tensile strength and yield strength, and the values are 271 and 205 MPa at room temperature, 205 MPa and 150 MPa at 250 degrees C, respectively. Which are about 2 times higher than those of Mg-8Gd-0.6Zr alloy. The improved hardness and strength are mainly attributed to the fine dispersiveness Of Mg5RE and Mg12RE precipitates in the alloy.

Synthesis of bis(amine anhydride)s for novel high T(g)s and organosoluble poly(amine imide)s by palladium-catalyzed amination of 4-chlorophthalide anhydride

Two novel bis(amine anhydride)s, NN-bis(3,4-dicarboxyphenyl)aniline dianhydride (I) and N,N-bis(3,4-dicarboxyphenyl)-p-tert-butylaniline (II), were synthesized from the palladium-catalyzed amination reaction of N-methyl-protected 4-chlorophthalic anhydride with arylamines, followed by alkaline hydrolysis of the intermediate bis(amine-phthalimide)s and subsequent dehydration of the resulting tetraacids. The X-ray structures of anhydride I and II were determined. The obtained dianhydride monomers were reacted with various aromatic diamines to produce a series of novel polyimides. Because of the incorporation of bulky, propeller-shaped triphenylamine units along the polymer backbone, all polyimides exhibited good solubility in many aprotic solvents while maintaining their high thermal properties. These polymers had glass transition temperatures in the range of 298-408 degrees C. Thermogravimetric analysis showed that all polymers were stable, with 10% weight loss recorded above 525 degrees C in nitrogen.The tough polymer films, obtained by casting from solution, had tensile strength, elongation at break, and tensile modulus values in the range of 95-164 MPa, 8.8-15.7%, and 1.3-2.2 GPa, respectively.

Synthesis and properties of novel soluble polyimides having a spirobisindane-linked dianhydride unit

A new synthetic procedure was elaborated allowing the preparation of semiaromatic dianhydride. N-Methyl protected 4-chlorophthalic anhydride was nitrated with HNO3 to produce N-methyl-4-chloro-5-nitrophthalimide (1). The aromatic nucleophilic substitution reaction between 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1-spirobisindane and 1 afforded spirobisindane-linked bis(N-methylphthalimide) (2), which was hydrolyzed and subsequently dehydrated to give the corresponding dianhydride (3). The latter was polymerized with five different aromatic diamines to afford a series of aromatic polyimides. The properties of polyimides such as inherent viscosity, solubility, UV transparency and thermal stability were investigated to illustrate the contribution of the introduction of spirobisindane groups into the polyimide backbone. The resulting polyimides were readily soluble in polar solvents such as chloroform, THF and N-methyl-2-pyrrolidone. The glass-transition temperatures of these polyimides were in the range of 254-292 degrees C. The tensile strength, elongation at break, and Young's modulus of the polyimide film were 68.8-106.6 MPa, 5.9-9.8%, 1.7-2.0 GPa, respectively. The polymer films were colorless and transparent with the absorption cutoff wavelength at 286-308 nm.