3{1-[2-(-3-羟基-1-甲基-2-亚丁烯氨基)-苯亚氨基]-乙基}4-甲硫基-2,4-戊二烯-2-醇的不对称Schiff碱镍(Ⅱ)配合物的合成、结构和性质

由 5-(2-乙酰基-1-甲硫基-3-羰基-亚丁基)-丙二酸亚异丙酯 (1)与邻苯二胺及乙酸镍()经一步反应合成了3{1-[2-( -3-羟基-1-甲基-2-亚丁烯氨基)-苯亚氨基 ]-乙基} 4-甲硫基-2,4-戊二烯-2-醇(3)的不对称四齿 Schiff碱镍()配合物(2),X射线衍射结果表明,配合物 2属单斜晶系,P21/C空间群.a=1.1476(2)nm,b=1.1782(2)nm,c=1.4810(3)nm;β=111.73(2)°,V=1.8602(7)nm3,Z=4,Rf=0.0535.电化学(循环伏安)测定结果表明,该配合物在测定条件下(阳极峰电位为1.1)发生了不可逆的氧化-还原反应.

Synthesis and structure of iron complex with 1,2-dithiolate-1,2-dicarba-closo-dodecaborane [Li(THF)(4)][Fe(S2C2B10H10)(2)(THF)]

The crystal of complex [Li(THF)(4)][Fe(S2C2B10H10)(2)(THF)] 3 belongs to monoclinic, space group P2(1) with a = 11.964(2), b = 16.527(3), c = 12.554(3) Angstrom,beta = 108.70(3)degrees, V= 2351.3(8) Angstrom(3), Z = 2, M-r = 835.95, D-c = 1.181 g/cm(3), mu (MoKalpha) = 5.30 cm(-1), f(000) = '874, R = 0.0622 and Rw 0.1538 for 1641 observed reflections with I > 2sigma(I). The ionic complex,of 3 contains the square pyramidal anion of [Fe(S2C2B10H10)(2)(THF)](-) and the tetrahedral cation of [Li(THF)(4)](+). The iron is 5-coordinated and located in the square pyramidal configuration. The iron atom and the four sulfur atoms are almost coplanar. The Lithium atom is coordinated with four oxygen atoms of four THF molecules and located in a tetrahedral configuration.

聚苯胺对2,5-二巯基-1,3,4-噻二唑氧化还原反应的电化学催化作用的循环伏安研究

研究了聚苯胺 ( PAn)膜电极在 2 ,5-二巯基 -1 ,3 ,4 -噻二唑 ( DMc T)溶液中电化学处理或浸泡后的循环伏安 ( CV)曲线的变化规律 .实验结果表明 ,PAn膜电极在 DMc T溶液中进行电化学处理或浸泡过程可使DMc T进入 PAn膜内部与 PAn形成复合物 .PAn对 DMc T的电化学催化作用可能和二者之间形成的电子给体 -受体复合物有关 .该复合物的电化学氧化还原特性不同于 PAn和 DMc T,其氧化还原反应速率和可逆性均优于 DMc T

三苯基锡-2-(1,2-亚乙二硫)亚甲基-3-羰基-5-芳基-4-戊烯酸酯的合成及晶体结构

由2-(1,2-亚乙二硫)亚甲基-3-羰基-5-芳基-4-戊烯酸与三苯基氢氧化锡反应,合成了九个标题化合物3.用X射线衍射法测定了3b的晶体结构.该晶体属三斜晶系,空间群Pl,α=0.9074(2)nm,b=1.6809(3)nm,c=2.1834(4)nm,α=77.57(3)°,β=88.04(3)°,γ=89.47(3)°,V=3.2503nm~3,Z=2;R=0.0592.由锡氧原子间距离可推测,该晶体中羧酸根作为双齿配体与锡原子形成了分子内五配位结构.

三环己基锡-2-(1,2-亚乙二硫)亚甲基-3-羰基-5-芳基-4-戊烯酸酯的结构研究

合成了 3个三环己基锡 -2 -( 1 ,2 -亚乙二硫 )亚甲基 -3-羰基 -5 -芳基 -4 -戊烯酸酯化合物 .用 IR,1 H NMR,1 3 C NMR和 1 1 9Sn NMR光谱及 X射线衍射对所合成的化合物进行了表征 .结果表明标题化合物为四配位、具有畸变四面体结构的锡酯类化合物

Effect and mechanism in compatibilization of poly(styrene-b-2-ethyl-2-oxazoline) diblock copolymer in poly(2,6-dimethyl-1,4-phenylene oxide) poly(ethylene-ran-acrylic acid) blends

The compatibilization effect of poly(styrene-b-2-ethyl-2-oxazoline) diblock copolymer, P(S-b-EOx), on immiscible blends of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) and poly(ethylene-co-acrylic acid) (EAA) is examined in terms of phase structure and thermal, rheological and mechanical properties, and its compatibilizing mechanism is investigated by Fourier-transform infrared spectroscopy. The block copolymer, synthesized by a mechanism transformation copolymerization, is used in solution blending of PPO/EAA. Scanning electron micrographs show that the blends exhibit a more regular and finer dispersion on addition of a small amount of P(S-b-EOx). Thermal analysis indicates that the grass transition of PPO and the lower endothermic peal; of EAA components become closer on adding P(S-b-EOx), and the added diblock copolymer is mainly located at the interface between the PPO and EAA phases. The interfacial tension estimated by theological measurement is significantly reduced on addition of a small amount of P(S-b-EOx). The tensile strength and elongation at break increase with the addition of the diblock copolymer for PPO-rich blends, whereas the tensile strength increases but the elongation at break decreases for EAA-rich blends. This effect is interpreted in terms of interfacial activity and the reinforcing effect of the diblock copolymer, and it is concluded that the diblock copolymer plays a role as an effective compatibilizer for PPO/EAA blends. The specific interaction between EAA and polar parts of P(S-b-EOx) is mainly hydrogen bonding. (C) 1998 Elsevier Science Ltd. All rights reserved.

Compatibilizing effect of polystyrene-block-poly(4-vinylpyridine) for poly(2,6-dimethyl-1,4-phenyleneoxide) chlorinated polyethylene blends

The compatibilizing effect and mechanism of compatibilization of the diblock copolymer polystyrene-block-poly(4-vinylpyridine) P(S-b-4VPy) on immiscible blends of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO)/chlorinated polyethylene (CPE) were studied by means of scanning electron microscopy (SEM), differential scanning calorimetry (DSC), mechanical properties and FTIR measurements. The block copolymer was synthesized by sequential anionic polymerization and melt-blended with PPO and CPE. The results show that the P(S-b-4VPy) added acts as an effective compatibilizer, located at the interface between the PPO and the CPE phase, reducing the interfacial tension, and improving the interfacial adhesion. The tensile strength and modulus of all blends increase with P(S-b-4VPy) content, whereas the elongation at break increases for PPO-rich blends, but decreases for CPE-rich blends. The polystyrene block of the diblock copolymer is compatible with PPO, and the poly(4-vinylpyridine) block and CPE are partially miscible.

Gas permeation properties of copolyimides from 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride and 2,2-bis(3,4-dicarboxyphenyl)hexafluoroisopropane dianhydride

A series of aromatic copolyimides was prepared from 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride (HQDPA) and 2,2-bis(3,4-dicarboxyphenyl)hexafluoroisopropane dianhydride (6FDA) with 3,3'-dimethyl-4,4'-methylene dianiline (DMMDA) by a chemical imidization. The gas permeability coefficients of the copolyimides to H-2, CO2, O-2, N-2 and CH4 were measured under 7 atm. pressure. The fractional free volume of 6FDA-DMMDA is larger than that of HQDPA-DMMDA, while the chain segmental mobility of 6FDA-DMMDA is lower than that of HQDPA-DMMDA. The gas permeability of 6FDA-DMMDA is much higher than that of HQDPA-DMMDA but the permselectivity of 6FDA-DMMDA for H-2, CO2, O-2, N-2 over CH4 is lower than that of HQDPA-DMMDA. The experimental values of the gas permeability coefficients of the copolyimides are in satisfactory agreement with the values estimated from the gas permeability coefficients of the constituent homopolyimides and their weight fractions.

Structure/permeability and permselectivity relationship of polyetherimides from 1,4-bis(3,4-dicarboxyphenoxy) benzene dianhydride .2.

Gas permeability coefficients of a series of aromatic polyetherimides, which were prepared from 1,4-bis(3,4-dicarboxyphenoxy) benzene dianhydride (HQDPA) with various aromatic diamines, to H-2, O-2 and N-2 have been measured under 7 atm and at the temperature range 30-100 degrees C. A significant change in the permeability and permselectivity resulting from the systematic variation in chemical structure of the polyetherimides was found. Among the polyetherimides, that were prepared from phenylenediamine and methyl substituted phenylenediamines, the increase of permeability is accompanied by a decrease of permselectivity. The polyetherimides that were prepared from 3,5-diaminobenzoic esters have lower permselectivity than the others. However, the polyetherimide from 3,5-diaminobenzoic acid possesses much higher permselectivity than the others due to cross-linking. Copyright (C) 1996 Elsevier Science Ltd

A HIGH-RESOLUTION SOLID-STATE NMR-STUDY OF THE MISCIBILITY, MORPHOLOGY, AND TOUGHENING MECHANISM OF POLYSTYRENE WITH POLY(2,6-DIMETHYL-1,4-PHENYLENE OXIDE) BLENDS

An extended Goldman-Shen pulse sequence was used to observe indirectly the proton spin diffusion in the blends of polystyrene (PS) with poly(2,6-dimethyl-1,4-phenylene oxides) (PPO). The results indicate that the average distance between PS and PPO is less than 5 angstrom in the intimately mixed phase, but there are heterogeneous domains on a 100-angstrom scale. The data of spin relaxation of carbons, T1(C), for homopolymers and their blends suggest that there is a strong pi-pi electron conjugation interaction between the aromatic rings of PS and those of PPO, while the aromatic rings of PPO drive the aromatic rings of PS to move cooperatively. It is the cooperative motion that markedly improves the impact strength of PS.

COMPATIBILIZING EFFECT OF POLY(ETHYLENE OXIDE)-B-POLYSTYRENE-B-POLY(ETHYLENE OXIDE) IN PHENOLPHTHALEIN POLY(ETHER ETHER KETONE) POLY(2,6-DIMETHYL-1,4-PHENYLENE OXIDE) BLENDS

The morphology and mechanical behaviour of phenolphthalein poly(ether ether ketone) (PEK-C)/poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) blends has been investigated. A poly(ethylene oxide)-b-polystyrene-b-poly(ethylene oxide) (PEO-PS-PEO) triblock copolymer was used as compatibilizer. It was found that PEO-PS-PEO has a compatibilizing effect on the PEK-C/PPO blends. The addition of PEO-PS-PEO to the blends greatly improves phase dispersion and interfacial interfacial adhesion and also enhances the ultimate tensile strength and Young's modulus at compositions ranging from 30 to 70% PEK-C. However, all the values of the ultimate tensile strength within the whole composition range are lower than those expected by simple additivity, probably owing to the poor mechanical properties of PEO-PS-PEO copolymer.

1-(4-fluorophenyl)-2-{4-phenyl-5-[(1H-1,2,4-triazol-1-yl) methyl]-4H-1,2,4-triazol-3-ylsulfanyl}ethanone

The crystal structure of the title compound, C19H15FN6OS, is stabilized by a weak intermolecular C-(HN)-N-... hydrogen-bond interaction.

Structure and biological activities of 2-(1,3-dithiolan-2-ylidene)-1-phenyl-2-(1,2,4-triazol-1-yl) ethanone

In order to find leading compounds with an excellent fungicidal activity, the tide compound 2-(1,3-dithiolan-2-yl-idene) -1-phenyl-2-(1,2,4-triazol-1-yl) ethanone was synthesized according to the biological isosterism and its structure was confirmed by means of IR, MS, H-1 NMR and elemental analysis. The single crystal structure of the tide compound was determined by X-ray diffraction. The preliminary biological test shows that the synthesized compound exhibits some biological activities.

Synthesis, crystal structure and biological activities of N '-(4-methoxybenzylidene)-2-(1H-1,2,4-triazol-1-yl) acetohydrazide

The title compound, N'-(4-methoxybenzylidene)-2-(1H-1,2,4-triazol-1-yl)acetohydrazide, was synthesized and its structure was confirmed by means of IR, MS,H-1 NMR and elemental analysis. The single crystal structure of the title compound was determined by X-ray diffraction. The preliminary biological test shows that the synthesized compound has a low antifungal activity.

Synthesis and. crystal structure of N '-(4-fluorobenzylidene)-2-(1H-1,2,4-triazole-1-yl) acetohydrazide

N'-(4-fluorobenzylidene)-2-(1H-1 2,4-triazole-1-yl) acetohydrazide was synthesized by the reaction of 4-fluorobenzaldehyde with 2-(1H-1 2,4-triazole-1-yl) acetohydrazide. The structure was confirmed via elemental analysis, MS, H-1 NMR, IR, and X-ray diffraction. It crystallized in a monoclinic system with space group P2 (1) a = 0.4905 (1) nm, b = 0.8160 (2) nm, c = 1.4105 (3) nm, beta = 93.33 (3)degrees, Z = 2, V = 0.5636 (2) nm(3), D-c = 1.457 Mg/m(3), mu = 0.112 mm(-1), F(000) = 256, and final R-1 = 0.0685. Several intermolecular hydrogen-bond interactions existed in the crystal structure, facilitating the stabilization of the compound.