(R,R)-DPEN-modified Ru/gamma-Al2O3 - An efficient heterogeneous catalyst for enantioselective hydrogenation of acetophenone

An efficient enantioselective catalyst of 5 wt.% Ru/-gamma-Al2O3 modified with R,R-1,2-diphenylethylene-diamine ((R,R)-DPEN) for the hydrogenation of a non-activated aromatic ketone of acetophenone has been investigated, a relatively high enantiomeric excess (ee) of 60.5% was obtained at both the conversion and selectivity larger than 99%, it was about three times higher than the ee values reported up to now for acetophenone hydrogenation with the supported transition metal catalysts modified by chiral reagents. The influences of some reaction parameters such as phosphine ligand, substrate/catalyst/modifier molar ratios, base, solvent, pressure and reaction temperature have been discussed. The chiral modifier of (R,R)-DPEN was very important in controlling the enantioselectivity through adsorption competing with other substrates on the surface of active metal species. The phosphine ligand and base were also important and indispensable in the present reaction.

Synthesis and characterization of novel sulfonated polyimides from 1,4-bis(4-aminophenoxy)-naphthyl-2,7-disulfonic acid

A novel sulfonated diamine monomer, 1,4-bis(4-aminophenoxy)-naphthyl-2,7-disulfonic acid (BAPNDS), was synthesized. A series of sulfonated polyimide copolymers were prepared from BAPNDS, 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA) and nonsulfonated diamine 4,4'-diaminodiphenyl ether (ODA). Flexible, transparent, and mechanically strong membranes were obtained. The membranes displayed slightly anisotropic membrane swelling. The dimensional change in thickness direction was larger than that in planar. The novel SPI membranes showed higher conductivity, which was comparable or even higher than Nafion 117. Membranes exhibited methanol permeability from 0.24 x 10(-6) to 0.80 X 10(-6) cm(2)/s at room temperature, which was much lower than that of Nafion (2 x 10-6 CM2/s). The copolymers were thermally stable up to 340 degrees C. These preliminary results have proved its potential availability as proton-exchange membrane for PEMFCs or DMFCs.

Synthesis and properties of novel sulfonated polyimides containing binaphthyl groups as proton-exchange membranes for fuel cells

A novel sulfonated diamine monomer, 2,2'-bis(p-aminophenoxy)-1,1'-binaphthyl-6,6'-disulfonic acid (BNDADS), was synthesized. A series of sulfonated polyimide copolymers containing 30-80 mol % BNDADS as a hydrophilic component were prepared. The copolymers showed excellent solubility and good film-forming capability. Atomic force microscopy phase images clearly showed hydrophilic/hydrophobic microphase separation. The relationship between the proton conductivity and degree of sulfonation was examined. The sulfonated polyimide copolymer with 60 mol % BNDADS showed higher proton conductivity (0.0945-0.161 S/cm) at 20-80 degrees C in liquid water. The membranes exhibited methanol permeability from 9 x 10(-8) to 5 X 10(-7) cm(2)/s at 20 degrees C, which was much lower than that of Nafion (2 x 10(-6) cm(2)/s). The copolymers were thermally stable up to 300 degrees C. The sulfonated polyimide copolymers with 30-60 mol % BNDADS showed reasonable mechanical strength; for example, the maximum tensile strength at break of the sulfonated polyimide copolymer with 40 mol % BNDADS was 80.6 MPa under high moisture conditions. The optimum concentration of BNDADS was found to be 60 mol % from the viewpoint of proton conductivity, methanol permeability, and membrane stability.

Isomeric polyimides

This review deals with polyimides based on isomeric dianhydrides and diamines, and with chiral polyimides. First, however, a summary is presented of recent work on the synthesis of isomeric dianhydrides, the reaction of mellophanic dianhydride with diamines, and the tendency toward cyclization in reactions of some dianhydrides and diamines. Then turning to polymers, the discussion covers solubility, thermal and dielectric properties, permeability and permselectivity for gas separation, and rheology of isomeric polyimides. Several useful general rules have been found: i.e. the glass transition temperature of polyimides based on isomeric dianhydrides with a given diamine decreases in the order 3,3'- > 3,4'- > 4,4-dianhydride if the polymers are of comparable molecular weight, whereas the thermal stability and the T-beta/T-g ratio (in absolute temperatures) increase in the order of 3,3'- < 3,4'- < 4,4'-dianhydride. Polyimides from 3,3'- or 3,4'-dianhydride have higher solubility than those from 4,4'-dianhydride. Polyimides from 3,4'-dianhydrides exhibit much lower melt viscosity than those from the other isomeric anhydrides. The dielectric constants of polyimides derived from m,m'-diamines are lower than those from p,p'-diamines. Polyimides based on 3,3'- or 3,4'-dianhydrides have higher permeability and slightly lower permselectivity than polyimides based on 4,4'-dianhydrides.

Hydrazine-based polyimides from isomeric bis(chlorophthalimide)s

3,3-Dichloro-N,N'-biphthalimide (3,3'-DCBPI), 3,4'-dichloro-N,N'-biphthalimide (3,4'-DCBPI), and 4,4'-dichloro-N,N'X-biphthalimide (4,4'-DCBPI) were synthesized from 3- or 4-chlorophthalic anhydrides and hydrazine in glacial acetic acid. The yield of 3,3'-DCBPI (90%) was much higher than that of 4,4'-DCBPI (33%) because of the better stability of the intermediate, 3-chloro-N-aminophthalimide, and 3,3'-DCBPI. A series of hydrazine-based polyimides were prepared from isomeric DCBPIs and 4,4-thiobisbenzenethiol (TBBT) in N,N-dimethylacetamide in the presence of tributylamine. Inherent viscosity of these polymers was in the range of 0.51-0.69 dL/g in 1-methyl-2-pyrrolidinone (NMP) at 30 degrees C. These polyimides were soluble in 1,1,2,2-terachloroethane, NMP, and phenols. The 5% weight-loss temperatures (T(g)s) of the polymers were near 450 degrees C in N-2. Their glass-transition temperatures (T(g)s) determined by dynamic mechanical thermal analysis and differential scanning calorimetry increased according to the order of polyimides based on 4,4'-DCBPI, 3,4'-DCBPI, and 3,3'-DCBPI. The hydrolytic stability of these polymers was measured under acid, basic, and neutral conditions and the results indicated that the order was 3,3'-DCBPI/TBBT > 3,4'-DCBPI/TBBT > 4,4'-DCBPI/TBBT.

Modeling of organic light-emitting diodes with graded concentration in the emissive multilayer

We model the electrical behavior of organic light-emitting diodes whose emissive multilayer is formed by blends of an electron transporting material, tris-(8-hydroxyquinoline) aluminum (Alq(3)) and a hole transporting material, N,N-'-diphenyl-N,N-'-bis(1,1(')-biphenyl)-4,4-diamine. The multilayer is composed of layers of different concentration. The Alq(3) concentration gradually decreases from the cathode to the anode. We demonstrate that these graded devices have higher efficiency and operate at lower applied voltages than devices whose emissive layer is made of nominally homogeneous blends. Our results show an important advantage of graded devices, namely, the low values of the recombination rate distribution near the cathode and the anode, so that electrode quenching is expected to be significantly suppressed in these devices.

Polyimides derived from 3,3 '-bis(N-aminophthalimide)

A novel diamine, 3,3'-bis(N-aminophthalimide) (BAPI), was prepared from 3,3'-bis(N-phenylphthalimide). Its structure was determined via IR, H-1 NMR, N-15 NMR, elemental analysis, and single-crystal X-ray diffraction analysis. A series of homo- and copolyimides were synthesized by a conventional one-step method in p-chlorophenol. The characteristic IR absorption bands of hydrazine-based imide groups were near 1780, 1750, 1350, 1100, and 730 cm(-1). The polymers showed good solubility in polar aprotic solvents and phenols at room temperature. The temperatures of 5% weight loss (T-5%) of the polyimides ranged from 495 to 530 degrees C in air. DMTA analyses indicated that the glass-transition temperatures (Tgs) of the polyimides were in the range 371-432 degrees C. These polymers had cutoff wavelengths between 350 and 400 nm. The polyimide films of 6FDA/BAPI and 4,4'-HQPDA/BAPI were colorless; other films were pale yellow or yellow.

Polyimides from isomeric diphenylthioether dianhydrides

3,3',4,4'-Diphenylthioether dianhydride (4,4'-TDPA), 2,3,3',4'-diphenylthioether dianhydride (3,4'-TDPA), and 2,2',3,3-diphenylthioether dianhydride (3,3'TDPA) were synthesized from 3-chlorophthalic anhydride and 4-chlorophthalic anhydride. A series of polyimides derived from the isomeric diphenylthioether dianhydrides with several diamines were prepared. The properties, such as the solubility, thermal and mechanical behavior, dynamic mechanical behavior, wide-angle X-ray diffraction, and permeability to some gases, were compared among the isomeric polyimides. Both 3,3'-TDPA- and 3,4-TDPA-based polyimides had good solubility in polar aprotic solvents and phenols. The 5% weight loss temperatures of all the obtained polyimides was near 500 degrees C in nitrogen. The glass-transition temperatures decreased according to the order of the polyimides based on 3,3'-TDPA, 3,4'-TDPA, and 4,4'-TDPA. The 3,4'-TDPA-based polyimides had the best permeability and lowest permselectivity, whereas the 4,4'-TDPA-based polyimides had the highest permselectivity and the lowest permeability of the three isomers. Furthermore, the rheological properties of thermoplastic polyimide resins based on the isomeric dipbenylthioether dianhydrides were investigated, and they showed that polyimide 3,4'-TDPA/4,4-oxydianiline had the lowest melt viscosity among the isomers; this indicated that the melt processibility had been greatly improved.

Synthesis and properties of soluble polyimides based on isomeric ditrifluoromethyl substituted 1,4-bis(4-aminophenoxy)benzene

A new fluorinated diamine monomer, [1,4-bis(4-amino-3-trifluoromethylphenoxy)benzene (2)], and a known isomeric analog 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene (3) were synthesized. A series of organosoluble polyimides Ia-d and IIa were prepared from the diamines (2, 3) and dianhydrides (a-d) by a high-temperature one-step method. The effects of the trifluoromethyl substituents on the properties of polyimides were evaluated through the study of their soluble, thermal, optical, and gas permeability properties. Polyimides (Ia-d) had glass transition temperatures between 229 and 279 degrees C, and the temperatures at 5% weight loss ranged from 510 to 533 degrees C under nitrogen. These polyimides could be cast into flexible and tough membranes from DMAc solutions. The membranes had tensile strengths in the range of 137-169 MPa, tensile modulus in the range of 1.6-2.2 GPa and elongations at break from 11% to 14%. The polyimide la with trifluoromethyl groups ortho to the imide nitrogen exhibited enhanced gas permeability, solubility, transparency, and thermal stability compared with the isomeric polyimide IIa with the CF3 group meta to the imide nitrogen.

High efficiency white organic light-emitting diodes based on double recombination zones

A multilayer white organic light-emitting diode (OLED) with high efficiency was present. The luminescent layer was composed of a red dye 4-(dicyanomethylene)-2-t-butyle-6-(1,1,7,7-tetra-methyljulolidyl-9-enyl)-4H-pyran (DCJTB) doped into NN-bis-(1-naphthyl)-N,N-diphenyl-1,1-biphenyl-4-4-diamine (NPB) layer and a blue-emitting 9,10-bis-(beta-naphthyl)-anthrene (DNA) layer. Red and blue emission, respectively, from DCJTB:NPB and DNA can be obtained by effectively controlling the thicknesses of DCJTB:NPB and DNA layers, thus a stable white light emission was achieved. The device turned on at 3.5 V, and the maximum luminance reached 16000 cd/m(2) at 21 V. The maximum current efficiency and power efficiency were 13.6 cd/A and 5.5 lm/W, respectively.

Syntheses and properties of novel polyimides derived from 2-(4-aminophenyl)-5-aminopyrimidine

2-(4-Aminophenyl)-5-aminopyrimidine (4) is synthesized via a condensation reaction of vinamidium salts and amidine chloride salts, followed by hydrazine palladium catalyzed reduction. A series of novel homo- and copolyimides containing pyrimidine unit are prepared from the diamine and 1,4-phenylenediamine (PDA) with pyromellitic dianhydride (PMDA) or 3,3',4,4'-biphenyl tertracarboxylic dianhydride (BPDA) via a conventional two-step thermal imidization method. The poly(amic acid) precursors had inherent viscosities of 0.97-4.38 dL/g (c = 0.5 g/dL, in DMAc, 30 degrees C) and all of them could be cast and thermally converted into flexible and tough polyimide films. All of the polyimides showed excellent thermal stability and mechanical properties. The glass transition temperatures of the resulting polyimides are in the range of 307-434 degrees C and the 10% weight loss temperature is in the range of 556-609 degrees C under air. The polyimide films possess strength at break in the range of 185-271 MPa, elongations at break in the range of 6.8-51%, and tensile modulus in the range of 3.5-6.46 GPa. The polymer films are insoluble in common organic solvents, exhibiting high chemical resistance.

Enhanced efficiency of light-emitting polymers through intra-molecular energy transfer

To enhance the photoluminescence and electroluminescence efficiency, light-emitting polymers with energy transferring chromophores including N,N,N'N'-phenylene-diamine, naphthalene-imide, oxadiazole, meta-phenylene vinylene are designed and synthesized.

Efficient red organic light-emitting devices based on a europium complex

An efficient organic light-emitting device using a trivalent europium (Eu) complex Eu(Tmphen)(TTA)(3) (TTA=thenoyltrifluoroacetone, Tmphen=3,4,7,8-tetramethyl-1,10-phenanthroline) as the dopant emitter was fabricated. The devices were a multilayer structure of indium tin oxide/N,N-diphenyl-N,N-bis(3-methylphenyl)-1,1-biphenyl-4,4-diamine (40 nm)/ Eu complex:4,4-N,N-dicarbazole-biphenyl (1%, 30 nm)/2,9-dimethyl,4,7-diphenyl-1,10phenanthroline (20 nm)/AlQ (30 nm)/LiF (1 nm)/Al (100 nm). A pure red light with a peak of 612 nm and a half bandwidth of 3 nm, which is the characteristic emission of trivalent europium ion, was observed. The devices show the maximum luminance up to 800 cd/m(2), an external quantum efficiency of 4.3%, current efficiency of 4.7 cd/A, and power efficiency of 1.6 lm/W. At the brightness of 100 cd/m(2), the quantum efficiency reaches 2.2% (2.3 cd/A).

Syntheses of biphenyl polyimides via nickel-catalyzed coupling polymerization of bis(chlorophthalimide)s

A facile method for the synthesis of biphenyl polyimides, which involves the nickel-catalyzed coupling of aromatic dichlorides containing imide structure in the presence of zinc and triphenylphosphine, has been developed. The polymerizations proceeded smoothly under mild conditions and produced biphenyl polyimides with inherent viscosities of 0.13-0.98 dL/g. The polymerizations of bis(4-chlorophthalimide)s with bulky side substituents gave high molecular weight polymers. Low molecular weight polymers from bis(4-chlorophthalimide)s containing rigid diamine moieties and bis(3-chlorophthalimide)s were obtained because of the formations of polymer precipitate and cyclic oligoimides, respectively. The effects of various factors, such as amount of catalyst, solvent volume, ligand, reaction temperature, and time, on the polymerization were studied. The random copolymerization of two bis(chlorophthalimide)s in varying proportions produced medium molecular weight material. The TgS of prepared polyimides were observed at 245-311 degreesC, and the thermogravimetry of polymers showed 10% weight loss in nitrogen at 470-530 degreesC.

Polyimides from isomeric oxydiphthalic anhydrides

2,2',3,3'-Oxydiphthalic dianhydride (2,2',3,3'-ODPA) and 2,3,3',4'-ODPA were synthesized from 3-chlorophthalic anhydride with 2,3-xylenol and 3,4-xylenol, respectively. Their structures were determined via single-crystal X-ray diffraction. A series of polyimides derived from isomeric ODPAs with several diamines were prepared in dimethylacetamide (DMAc) with the conventional two-step method. Matrix-assisted laser desorption/ionization time-of-flight spectra showed that the polymerization of 2,2',3,3'-ODPA with 4,4'-oxydianiline (ODA) has a greater trend to form cyclic oligomers than that of 2,3,3',4'-ODPA. Both 2,2',3,3'-ODPA and 2,3,3',4'-ODPA based polyimides have good solubility in polar aprotic solvents such as DMAc, dimethylformamide, and N-methylpyrrolidone. The 5% weight-loss temperatures of all polyimides were obtained near 500 degreesC in air. Their glass-transition temperatures measured by dynamic mechanical thermal analysis or differential scanning calorimetry decreased according to the order of polyimides on the basis of 2,2',3,3'-ODPA, 2,3,3',4'-ODPA, and 3,3',4,4'-ODPA. The wide-angle X-ray diffraction of all polyimide films from isomeric ODPAs and ODA showed some certain extent of crystallization after stretching. Rheological properties revealed that polyimide (2,3,3',4'-ODPA/ODA) has a comparatively lower melt viscosity than its isomers, which indicated its better melt processability.