Host (nanocavity of zeolite-Y)/guest (Mn(II), Co(II), Ni(II) and Cu(II) complexes of pentadendate Schiff-base ligand) nanocomposite materials (HGNM): application in the heterogeneous oxidation of cyclohexene

Transition metal (M = Mn(II), Co(II), Ni(II) and Cu(II)) complexes with pentadendate Schiff-base ligand; N,N′-bis(salicylidene)-2,6-pyridinediaminato, H₂ [sal-2,6-py]; was entrapped in the nanocavity of zeolite-Y by a two-step process in the liquid phase: (i) adsorption of bis(salicylaldiminato)metal(II); [M(sal)₂]-NaY; in the supercages of the zeolite, and (ii) in situ Schiff condensation of the metal(II) precursor complex with the corresponding 2,6-pyridinediamine; [M(sal-2,6-py)]-NaY. The new materials were characterised by several techniques: chemical analysis, spectroscopic methods (DRS, BET, FTIR and UV/Vis), conductometric and magnetic measurements. Analysis of the data indicates that the M(II) complexes are encapsulated in the nanodimensional pores of zeolite-Y and exhibit different from those of the free complexes, which can arise from distortions caused by steric effects due to the presence of sodium cations, or from interactions with the zeolite matrix. The Host–Guest Nanocomposite Materials (HGNM); [M(sal-2,6-py)]-NaY; catalyzes the oxidation of cyclohexene with tert-butylhydroperoxide (TBHP). Oxidation of cyclohexene with HGNM gave 2-cyclohexene-1-one, 2-cyclohexene-1-ol and 1-(tert-butylperoxy)-2-cyclohexene. [Mn(sal-2,6-py)]-NaY shows significantly higher catalytic activity than other catalysts.     

MCM-41-supported NNO type Schiff base complexes: a highly selective heterogeneous nanocatalyst for esterification,Diels–Alder and aldol condensation

Solid catalysts have been synthesized by anchoring transition metal complexes into organically modified MCM-41. First, the surface of Si-MCM-41 was modified with 3-aminopropyl-triethoxysilane (3-APTES), the imine group of which upon condensation with DFP (4-methyl-2,6-diformylphenol) affords a N₂O-type Schiff base moiety in the mesoporous matrix. The Schiff base moieties were used to anchor Ni (II) and Cu (II) ions. The prepared catalyst have been characterized by DRS (Diffuse Reflectance Spectroscopy), FTIR (Fourier transform infrared) spectroscopy, small-angle X-ray diffraction (SAX), FESEM (Field Emission Scanning Electron Microscope), EDX (Energy-dispersive X-ray spectroscopy) and nitrogen sorption studies. The decrease of crystallinity in the multistep synthesis procedure, as evidenced by SAX (Small-angle X-ray) measurements, was observed. The prepared materials proved to be efficient catalysts for organic transformations such as esterification, Diels–Alder and Aldol condensation at ambient conditions. The immobilized complex does not leach or decompose during the catalytic reactions, showing practical advantages over the free metal complex.     

Novel copolymers of trisubstituted ethylenes with styrene — 7. Methyl 2-cyano-3-dihalophenyl-2-propenoates

Summary Methyl 2-cyano-3-dihalophenyl-2-propenoates, R₂C₆H₃CH=C(CN)CO₂CH₃ (R₂= 2,4-difluoro, 2,5-difluoro, 2,6-difluoro, 3,4-difluoro, 3,5-difluoro, and 2-chloro-6-fluoro), were prepared by the piperidine catalyzed Knoevenagel condensation of corresponding disubstituted benzaldehydes and methyl cyanoacetate. Novel copolymers of the propenoates and styrene were prepared at equimolar monomer feed by solution copolymerization in the presence of a radical initiator. The order of relative reactivity (1/r ₁) was 2,5-difluoro (2.11) > 2,6-difluoro (1.84) > 3,5-difluoro (1.71) > 2,4-difluoro (1.4) > 3,4-difluoro (0.65) > 2-chloro-6-fluoro (0.59). The copolymers were characterized by IR, ¹H and ¹³C NMR, GPC, DSC and TGA. High glass transition temperatures of the copolymers compared that of polystyrene indicates a substantial decrease in chain mobility of the copolymers due to the high dipolar character of the trisubstituted ethylene monomer unit. Received: 12 June 2000/Revised version: 12 September 2000/Accepted: 12 September 2000     

Polyethylene‐b‐poly(ethylene glycol) diblock copolymers: New synthetic strategy and application

Polyethylene‐b‐poly (ethylene glycol) (PE‐b‐PEG) was successfully synthesized by a coupling reaction of hydroxyl‐terminated polyethylene (PE‐OH) and isocyanate‐terminated poly (ethylene glycol) (PEG‐NCO). PE‐OH was prepared by coordination chain transfer polymerization (CCTP) using 2,6‐bis[1‐(2,6‐diisopropylphenyl)imino ethyl] pyridine iron (II) dichloride /dry ethylaluminoxane (DEAO) /diethyl zinc (ZnEt₂) as catalyst and subsequent in situ oxidation with oxygen. The active centers of this catalyst system were counted, indicating that the active centers were more stable using DEAO as cocatalyst than using dry methylaluminoxane (DMAO) as cocatalyst. PEG‐NCO was synthesized through the condensation reaction of monomethylpoly(ethylene glycol) (PEG) with isophoronediisocyanate (IPDI). Subsequently, the thermal characterization, morphological characterization and the application of these diblock copolymers was investigated. The results indicated that the diblock copolymers were effective compatilizers for polyethylene/poly(ethylene glycol) blends. Meanwhile, they were excellent surface modification agents for polyethylene membrane and glass sheet, it can efficiently turn a hydrophobic surface into a hydrophilic surface, or vice versa. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42236.     

Synthesis and characterization of new aromatic poly(amide–imide)s based on 4‐aryl‐2,6‐bis(4‐trimellitimidophenyl) pyridines

New diimide–dicarboxylic acids, ie 4‐phenyl‐2,6‐bis(4‐trimellitimidophenyl)pyridine and 4‐p‐biphenyl‐2,6‐bis‐(4‐trimellitimidophenyl)pyridine, were synthesized by the condensation reaction of 4‐phenyl‐2,6‐bis(4‐aminophenyl)pyridine and 4‐p‐biphenyl‐2,6‐bis(4‐aminophenyl)pyridine with trimellitic anhydride in glacial acetic acid or dimethylformamide. The monomers were fully characterized by FT‐IR and NMR spectroscopies, and elemental analyses. A series of novel poly(amide–imide)s with inherent viscosities of 0.68–0.87 dl g^?1 was prepared from the two diimide–diacids with various aromatic diamines by direct polycondensation. The poly(amide–imide)s were characterized by FT‐IR and NMR spectroscopies. The λ_max data for the resulting poly(amide–imide)s were in the range of 260–292 nm. These polymers exhibited good solubilities in polar aprotic solvents. The 10 % weight loss temperatures are above 485 °C under a nitrogen atmosphere. Copyright © 2004 Society of Chemical Industry     

Synthesis and Characterization of Some Poly(1,2-Phenylenedithiocarbamate)–Metal Complexes

Poly(1,2-phenylenedithiocarbamate) (PPDTC) was prepared by the reaction of 2-aminothiophenol with carbon disulfide followed by condensation through the removal of H₂S gas. PPDTC was used as a ligand to prepare four poly(1,2-phenylenedithiocarbamate)–metal complexes of iron(II), cobalt(II), copper(II), and lead(II), by refluxing with the metal salts. The polymer and its metal complexes were investigated by elemental analyses, UV–visible and IR spectroscopy, inherent viscosity, and magnetic susceptibility. The DC electrical conductivity variation with the temperature in the range 298–498 K of PPDTC and its polymeric copper complex was measured. Both polymer and polymer metal complexes showed an increase in electrical conductivity with an increase in temperature: typical semiconductor behavior. The proposed structure of the complexes is (MLX₂·mH₂O) _n .     

Bimolecular formation of radicals by hydrogen transfer. 14. The uncatalyzed Transfer Hydrogenation of α-Methylstyrene by 2,6-disubstituted 9,10-Dihydroanthracenes

2,6-Dimethoxy-( 4a ), 2,6-bis(dimethylamino)-( 4b ), 2,6-dichloro- ( 4c ) and 2,6-dimethoxycarbonyl-9,10-dihydroanthracene ( 4d ) were prepared by conventional methods and used as hydrogen transfer donors to α-methylstyrene ( 5 ) between 290-350 °C. The mechanism followed second order kinetics and the rate constants were only slightly influenced by the solvent polarity and the type of substituents introduced. The activation parameters are also closely similar in the series with ΔS^≠ values between −21 and −28 cal/mol K. These results, together with the observation of a large isotope effect (k_H/k_D = 1.4–2.0 at 310–350 °C), suggest that the mechanism involves a primary kinetic H-atom-transfer from the donors to α-methylstyrene ( 5 ) in the rate determining step. The compounds 4a – 4d constitute a new probe for investigating polar effects on H-transfer reactions.     

Voltammetric investigation of polyelectrolyte-Cu(II) complexes

The complexation behaviours of poly(N-vinylcarbazole) (PNVCz), poly(acrylic acid) (PAA) poly(itaconic acid) (PIA) and their copolymers, synthesized by using different initial monomer compositions, with Cu(II) ions were investigated by the voltammetric technique. Their solutions were prepared in THF-water mixture according to the water-insoluble nature of PNVCz and its copolymers. The polymeric ligand-Cu(II) interactions, i.e. complex formations were studied as a function of copper ion concentration and copolymer composition. It was observed that although the cyclic voltammogram (CV) of Cu(II) alone in THF-water mixture was characterized by one redox wave, which has an irreversible nature, it became more reversible in the presence of polymer. Further, the CV results indicated the presence of two different electron transfer mechanisms, depending on the n _COOH/n _Cu(II) ratio and the carboxyl content of the copolymers.     

Inorganic–Organic Hybrid Materials of Zirconium and Aluminum and Their Usage in the Removal of Methylene Blue

Two novel inorganic–organic hybrid materials, Al-Pydca-3-APDEMS-H and Zr-Pydca-3-APDEMS-H, were prepared by the sol gel method in two steps. In the first step, Al(O^sBu)₂-Pydca and Zr(OPrⁿ)₃-Pydca complexes were prepared from the reactions of aluminum sec-butoxide Al(O^sBu)₃ and zirconium n-propoxide Zr(OPrⁿ)₄ with 2,6-pyridinedicarboxylic acid, respectively. After 3 h of stirring, 3-aminopropyldiethoxymethyl silane (3-APDEMS) and dilute hydrochloric acid were added to the Al(O^sBu)₂-Pydca and Zr(OPrⁿ)₃-Pydca mixtures to hydrolyze the reactions and to form condensation products. These hybrid products were characterized by a combination of Fourier-transform infrared (FT-IR) spectroscopy, powder X-ray diffraction (XRD), scanning electron microscope (SEM), energy-dispersive X-ray (EDX) spectroscopy, Brunauer–Emmett–Teller (BET) analysis, Barrett-Joyner-Halenda (BJH) and other analysis methods. These hybrid materials were used for the removal of methylene blue (MB), a cationic organic dye. The removal efficiency of hybrid materials was measured by UV–Vis spectroscopy.

     

Thermal and crystallization behaviors of polyethylene blends synthesized by binary late transition metal catalysts combinations

A series of reactor blends of linear and branched polyethylenes have been prepared, in the presence of modified methylaluminoxane, using a combination of 2,6‐bis[1‐(2,6‐dimethyphenylimino) pyridyl]‐cobalt(II) dichloride ( 1 ), known as an active catalyst for producing linear polyethylene, and [1,4‐bis(2,6‐diidopropylphenyl)] acenaphthene diimine nickel(II) dibromide ( 2 ), which is active for the production of branched polyethylene. The polymerizations were performed at various levels of catalyst feed ratio at 10 bar. The linear correlation between catalyst activity and concentration of catalyst 2 suggested that the catalysts performed independently from each other. The weight‐average molecular weights , crystalline structures, and phase structures of the blends were investigated, using a combination of gel permeation chromatography, differential scanning calorimetry, wide‐angle X‐ray diffraction, and small angle X‐ray scattering techniques. It was found that the polymerization activities and MWs and crystallization rate of the polymers took decreasing tendency with the increase of the catalyst 2 ratios, while melting temperatures (T_m), crystalline temperatures (T_c), and crystalline degrees took decreasing tendency. Long period was distinctly influenced by the amorphous component concentration. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 4188–4198, 2007     

1H nuclear magnetic resonance study of polyurethane prepolymers from toluene diisocyanate and polypropylene glycol

Polyurethane prepolymers prepared from toluene 2,4‐diisocyanate, toluene 2,6‐diisocyanate, and polypropylene glycol with a ratio between the isocyanate and hydroxyl groups equal to 2 were analyzed by ¹H nuclear magnetic resonance (NMR) spectroscopy in acetone‐d₆. Different temperatures and concentrations were used. Toluene 2,4‐dimethylurethane and toluene 2,6‐dimethylurethane were synthesized and used as model compounds to assign prepolymers signals. Measurements of spin–lattice relaxation time T₁ by “inversion recovery” experiments were carried out on toluene 2,4‐diisocyanate, toluene 2,6‐diisocyanate, toluene 2,4‐dimethylurethane, toluene 2,6‐dimethylurethane, and polyurethane prepolymers. Differences in T₁ times were used to interpret prepolymers spectra, by means of the strong observed effect on protons due to the presence of adjacent isocyanate groups. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 347–357, 2003     

Optical and electrochemical properties of oligo(1,5‐dialkoxynaphthalene‐2,6‐diyl)s with self‐assembled ordered structures in solid state

Oligo(1,5‐dialkoxynaphthalene‐2,6‐diyl)s were synthesized by Ni(cod)₂ (cod = 1,5‐cyclooctadiene)‐promoted condensation reactions of 1,5‐dialkoxy‐2,6‐dibromonaphthalenes. The UV–Vis, photoluminescence (PL), and powder X‐ray diffraction (XRD) measurements suggested that the oligomers have a self‐assembling ordered structure in the solid state. The oligomers underwent electrochemical oxidation (p‐doping), which occurred at lower potentials for films than for acetonitrile solutions containing [Et₄N]BF₄. This effect is caused by the longer π‐conjugation lengths of the oligomers in films, which was attributed to molecular self‐assembly leading to ordered structures in the solid state. The electrochemical reaction of the oligomers was accompanied by electrochromism. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41840.     

Alternating copolymerization and terpolymerization of vinyl‐substituted phenolic antioxidants with propene and carbon monoxide by a palladium(II)‐based catalyst: polyketones containing intramolecular stabilizers

The copolymerization and terpolymerization reactions of the vinyl‐substituted phenolic stabilizers, 6‐tert‐butyl‐2‐(1,1‐dimethylhept‐6‐enyl)‐4‐methylphenol, o‐allylphenol, 4‐methylstyrene‐2,6‐di‐tert‐butylphenol and 2,6‐di‐tert‐butyl‐4‐allylphenol, with propene and carbon monoxide, by using the solvent‐stabilized palladium(II ) phosphine complex [Pd(dppp)(NCCH₃)₂](BF₄)₂ (dppp, 1,3‐bis(diphenylphosphino)propane) as a catalyst precursor and methanol as a co‐catalyst, is described. The influence of functional α‐olefins/CO units, distributed statistically along the propene/carbon monoxide (P/CO) copolymer backbone, on the molecular weight, glass transition temperature (T_g), elastic behavior and stability of the high‐molecular‐weight P/CO copolymer has been investigated. Loss of both elasticity and transparency were observed upon incorporating o‐allylphenol as a termonomer. The terpolymers, which contain phenolic stabilizers, were shown to be more stable when compared to the stabilizer‐free polyketones. In contrast to the propene/carbon monoxide copolymer, no degradation was observed for the 2,6‐di‐tert‐butyl‐4‐allylphenol/P/CO terpolymer; instead, the molar masses increased. Copyright © 2004 Society of Chemical Industry     

Preparation of a Macroporous Silica-Based Multidentate Soft-Ligand Material and its Application in the Adsorption of Palladium and the Others

To separate Pd(II), a macroporous silica-based soft-ligand 2,6-bis(5,6-di(iso-butyl)-1,2,4-triazine-3-yl)pyridine (BDIBTP) material, BDIBTP/SiO₂-P, was synthesized by vacuum treatment. It was a multidentate chelating composite prepared by impregnation and immobilization of BDIBTP and 1-octanol molecules into the pores of the macroporous SiO₂-P particles with a mean diameter of 50 µm. 1-Octanol was used to modify BDIBTP through intermolecular interaction force. The adsorption of some typical fission products Zr(IV), Pd(II), La(III), Y(III), Ru(III), Rh(III), and Mo(VI) contained in highly active liquid waste (HLW) onto the BDIBTP/ SiO₂-P materials was investigated. It was carried out by examining the effects of contact time and the concentration of HNO₃ in the range of 0.3 M?7.0 M. BDIBTP/SiO₂-P showed excellent adsorption ability and high selectivity for Pd(II) over all of the tested metals. It was ascribed to the effective complexation of Pd(II) with BDIBTP/SiO₂-P. Consideration of the complexation of BDIBTP for minor actinides MAs(III), the possibility and feasibility of effective partitioning of Pd(II) and MAs(III) simultaneously from a simulated HLW were discussed. A new concept process entitled MPS for the MA(III) and Pd(II) Separation has been proposed.     

Highly Diastereoselective Synthesis of 2,6‐Di[1‐(2‐alkylaziridin‐1‐yl)alkyl]pyridines,Useful Ligands in Palladium‐Catalyzed Asymmetric Allylic Alkylation

C₂‐Symmetrical, enantiopure 2,6‐di[1‐(1‐aziridinyl)alkyl]pyridines (DIAZAPs) were prepared by a high‐yielding, three‐step sequence starting from 2,6‐pyridinedicarbaldehyde and (S)‐valinol or (S)‐phenylglycinol. The new compounds were tested as ligands in palladium‐catalyzed allylation of carbanions in different solvents. Almost quantitative yield and up to 99 % enantiomeric excess were obtained in the reactions of the enolates derived from malonate, phenyl‐ and benzylmalonate dimethyl esters with 1,3‐diphenyl‐2‐propenyl ethyl carbonate.     

Ethylene/1‐hexene copolymerization with supported Ziegler–Natta catalysts prepared by immobilizing TiCl3(OAr) onto MgCl2

Five titanium complexes TiCl₃(OAr) (Ar = C₆H₅? , 2,6‐Me₂C₆H₃? , 2,6‐i‐Pr₂C₆H₃? , 2,6‐t‐Bu₂C₆H₃? , 4‐Me‐2,6‐t‐Bu₂C₆H₃? ) were immobilized, respectively, on MgCl₂ in semibatch reaction to form supported catalysts for olefin polymerization. Comparing with the catalysts prepared by immobilizing TiCl₃(OAr) onto MgCl₂ in batch reaction, the catalysts prepared by semibatch reaction have lower titanium content and higher ArO/Ti ratio. The aryloxy‐containing catalysts studied in this work showed higher ethylene/1‐hexene copolymerization activity and higher 1‐hexene incorporation rate than the blank catalyst when activated by triisobutylaluminum. Similar effects of the aryloxy ligand were observed when the copolymerization is conducted in the presence of hydrogen. Introducing aryloxy ligand in the catalysts either by semibatch or batch reaction caused similar effects of enhancing copolymerization activity and α‐olefin incorporation rate. Mechanism of the effects of aryloxy ligand has been discussed. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41329.     

Synthesis and properties of novel poly(tetramethylsilnaphthylenesiloxane) derivatives

Novel poly(tetramethylsilnaphthylenesiloxane) derivatives were synthesized and characterized by differential scanning calorimetry (DSC), thermogravimetry (TG), and X-ray diffraction analyses. Poly(tetramethylsilnaphthylenesiloxane) derivatives were obtained by condensation polymerization of the corresponding disilanol derivatives, i.e. 1,4-, 1,5-, 2,6-, and 2,7-bis(dimethylhydroxysilyl)naphthalenes, which were prepared by the Grignard reaction using chlorodimethylsilane and the corresponding dibromonaphthalene derivatives followed by the hydrolyses, catalyzed by palladium on charcoal. The obtained poly(tetramethyl-1,5-silnaphthylenesiloxane) was insoluble in common organic solvents; however, the other polymers exhibited the good solubility in common organic solvents, such as tetrahydrofuran (THF), chloroform, dichloromethane, and toluene. The introduction of tetramethyl-1,5-silnaphthylenesiloxane units into the resulting polymer was confirmed by ¹H NMR spectrum of the copolymer obtained by condensation copolymerization of 1,5-bis(dimethylhydroxysilyl)naphthalene with 1,4-bis(dimethylhydroxysilyl)naphthalene. It was revealed from the DSC and X-ray diffraction measurements that poly(tetramethyl-1,5-silnaphthylenesiloxane) and poly(tetramethyl-2,6-silnaphthylenesiloxane) exhibited the crystallinity; however, poly(tetramethyl-1,4-silnaphthylenesiloxane) and poly(tetramethyl-2,7-silnaphthylenesiloxane) were amorphous. The glass transition temperature (T_g) and the temperature at 5% weight loss (T_d5) of poly(tetramethylsilnaphthylenesiloxane) derivatives with dimethylsilyl group at 1-position of the naphthylene moiety were higher than those at 2-position of the naphthylene moiety. The T_g and melting point (T_m) of the present polymers were higher than those of poly(tetramethyl-1,4-silphenylenesiloxane).     

Systematic study of ion-exchange properties and ligating behaviour of respropiophenone-formaldehyde copolymers

Respropiophenone-formaldehyde copolymers (RPP-F) were synthezised by the condensation of 2,4-dihydroxypropiophenone (respropiophenone (RPP)) and formaldehyde (F) in the presence of NaOH or H₂SO₄ as catalyst with varied molar ratios of reacting monomers. The copolymers were characterized by elemental analysis, IR spectra, viscosity, and TGA studies. Their M?_n was determined by nonaqueous conductometric titrations and vapour pressure osmometry (VPO). Chelation ion-exchange properties have also been studied employing the batch equilibration method. Polychelates of Cu(II), Ni(II), Co(II), Mn(II), Zn(II), VO(II), and UO₂(II) with RPP-F-AI copolymer were prepared. The analytical data agree with 1 : 2 metal-ligand stoichiometry. Elemental analysis, magnetic, spectral, and thermal properties of polychelates have been studied and probable structures are assigned to the polychelates. All the polychelates are amorphous powders, insoluble in common organic solvents.     

Crystal and molecular structure of copper(II)(pyridine-2,6-dicarboxylato)(2,6-dimethanolpyridine)

Copper(II)(pyridine-2,6-dicarboxylato)(2,6-dimethanolpyridine) has been prepared and studied by the single crystal X-ray diffraction methods at 293(2) K. The compound crystallises in an orthorhombic system, space group Pbcn with a=8.196(2), b=13.124(3), c=25.612(5) Å, and Z=8 (R=0.0374 for 3175 independent reflections with I>2σ(I)). Crystal structure analysis revealed that the copper(II) atom is surrounded by two non-equivalent terdentate ligands making up an ‘all-trans’ elongated octahedral arrangement. In consequence of Jahn–Teller distortion, considerable differences are found between the ligands for the pyridine-2,6-dicarboxylate anion with the values Cu–N 1.892(3), Cu–O 2.033(2) and 2.063(2) Å, while for the 2,6-dimethanolpyridine ligand the values are 1.943(3), 2.341(3) and 2.433(2) Å. There is a relationship between the Cu–L bond distances and the five-membered metallocyclic rings (O–Cu–N). The data are compared and discussed with those found in familiar CuL₂ compounds with the CuO₄N₂ chromophore. Based on the molecular structure, the electronic, IR and EPR spectra are discussed.     

Organosoluble,low‐dielectric‐constant fluorinated polyimides based on 2,6‐bis(4‐amino‐2‐trifluoromethylphenoxy)naphthalene

A novel fluorinated bis(ether amine) monomer, 2,6‐bis(4‐amino‐2‐trifluoromethylphenoxy) naphthalene, was prepared through the nucleophilic aromatic substitution reaction of 2‐chloro‐5‐nitrobenzotrifluoride and 2,6‐dihydroxynaphthalene in the presence of potassium carbonate, followed by catalytic reduction with hydrazine and Pd/C in ethanol. A series of novel trifluoromethylated polyimides were synthesized from the diamine with various commercially available aromatic tetracarboxylic dianhydrides using a two‐stage process with thermal imidization of poly(amic acid) films. Most of the resulting polyimides were highly soluble in a variety of organic solvents and could afford transparent and tough films via solution casting. These polyimides exhibited moderately high glass transition temperatures (T_gs) of 249–311 °C, high thermal stability and good mechanical properties. Low moisture (0.19–0.85 %), low dielectric constants (2.49–3.59 at 10 kHz), and low color intensity were also observed. For a comparative study, a series of analogous polyimides based on 2,6‐bis(4‐aminophenoxy)naphthalene were also prepared and characterized. Copyright © 2005 Society of Chemical Industry