Soluble and colorless polyimides from alicyclic diamines

A series of novel polyimides was synthesized from alicyclic diamines and various aromatic dianhydrides by one-step polymerization in m-cresol without a catalyst. The polymerization was conducted for 4 hours with refluxing, which was enough to obtain the polymers with high molecular weight. The inherent viscosities of the resulting polyimides were in the range of 0.30 similar to 1.29 dL/g. The prepared polyimides showed excellent thermal stabilities and good solubility. All the polymers were readily soluble in common organic solvents such as chloroform, tetrachloroethane (TCE), dimethylacetamide (DMAc), etc and the glass transition temperatures were observed at 199 to 311 degrees C. UV-visible spectra were obtained to measure the transparency of polymer films. All the polymers showed high transmission above 90% in the wavelength of 400 similar to 700 nm.

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.

Synthesis and characterization of novel polyimides from alicyclic dianhydride

New alicyclic Polyimides (PIs) were prepared from asymmetric alicyclic dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-cyclohexane-1,2-dicarboxylic anhydride (DOCDA) and the corresponding aromatic diamines such as p-phenylenediamine, m-phenylenediamine and oxydianiline etc. by the polycondensation in N-methyl-2-pyrrolidone (NMP) followed by chemical imidization as well as one step polyimidization in m-cresol in the presence of isoquinoline as a catalyst. The resulting PIs with glass transition temperatures ranging from 220 to 328 degrees C had the inherent viscosities within the range of 0.25 similar to 1.42 dL/g. These polymers were readily soluble in aprotic polar solvents such as NMP, dimethylacetamide (DMAc), dimethylesulfoxide (DMSO), etc. Furthermore, some of the polymers showed good solubility properties to common organic solvents like tetrahydrofurane and chlorform. Also, all of these polyimide films were tough, almost colourless, and transparent.

Synthesis, glucose uptake activity and structure-activity relationships of some novel glitazones incorporated with glycine, aromatic and alicyclic amine moieties via two carbon acyl linker

Three series of novel glitazones were designed and prepared by using appropriate synthetic schemes to incorporate glycine, aromatic and alicyclic amines via two carbon linker. Compounds were synthesized both under conventional and microwave methods. Nineteen out of twenty four synthesized compounds were evaluated for their in vitro glucose uptake activity using isolated rat hemi-diaphragm. Compounds, 6, 9a, 13a, 13b, 13c, 13f and 13h exhibited significant glucose uptake activity. Illustration about their synthesis and in vitro glucose uptake activity is described along with the structure activity relationships. (C) 2010 Elsevier Masson SAS. All rights reserved.

New triquinane-based host molecules : binding with diamines

Synthesis of several shape-specific hosts through heteroaromatic annulation on cis,syn,cis-triquinanedione 1 and X-ray crystal structure determination of one of them, 4a, is reported. Preliminary results of complexation between cleft 5a and diamines are reported.

Sulfates of organic diamines: hydrogen-bonded structures and properties

In order to investigate the supramolecular hydrogen-bonded networks and other structural features exhibited by compounds containing an organic cation and an inorganic anion, sulfates of the organic diamines, ethylenediamine (I), 1,3-diaminopropane (II), piperazine (III), and 1,4-diazabicyclo[2.2.2]octane (DABCO) (IV) have been prepared investigated by X-ray crystallography. While II, III, and IV crystallize in the centrosymmetric space group, Pbca, P2(1)/n, Pbcn, respectively, I crystallizes in the non-centrosymmetric space group, P4(1) exhibiting chirality and weak NLO properties. I-IV exhibit different types of supramolecular H-bonded networks involving the organic cation and the SO42- anion. The nature and strength of the H-bonding network vary from one compound to another, with the strongest network found in piperazinium sulfate, III, and the weakest in II. While in III, water molecules form part of the H-bonded network, they are present as guest molecules in the channels of IV. Thermal stability of the compounds as well as the infrared spectra reflect the stabilities of these H-bonded solids. (C) 2002 Editions scientifiques et medicales Elsevier SAS. All rights reserved.

Synthesis and properties of novel organosoluble polyimides derived from 1,4-bis[4-(3,4-dicarboxylphenoxy)]triptycene dianhydride and various aromatic diamines

A novel triptycene-based dianhydride, 1,4-bis[4-(3,4-dicarboxylphenoxy)]triptycene dianhydride, was prepared from 4-nitro-N-methylphthalimide and potassium phenolate of 1,4-dihydroxytriptycene (1). The aromatic nucleophilic substitution reaction between 4-nitro-N-methylphthalimide and I afforded triptycene-based bis(N-methylphthalimide) (2), which hydrolyzed and subsequently dehydrated to give the corresponding dianhydride (3). A series of new polyimides containing triptycene moieties were prepared from the dianhydride monomer (3) and various diamines in in-cresol via conventional one-step polycondensation method. Most of the resulting polyimides were soluble in common organic solvents, such as chloroform, THF, DMAc and DMSO. The polyimides exhibited excellent thermal and thermo-oxidative stabilities with the onset decomposition temperature and 10% weight loss temperature ranging from 448 to 486 degrees C and 526 to 565 degrees C in nitrogen atmosphere, respectively. The glass transition temperatures of the polyimides were in the range of 221-296 degrees C. The polyimide films were found to be transparent, flexible, and tough. The films had tensile strengths, elongations at break, and tensile moduli in the ranges 95-118 MPa, 5.3-16.2%, and 1.03-1.38 GPa, respectively. Wide-angle X-ray diffraction measurements revealed that these polyimides were amorphous.

Synthesis and properties of polyimides derived from cis- and trans-1,2,3,4-cyclohexanetetracarboxylic dianhydrides

Cis-1,2,3,4-cyclohexanetetracarboxylic dianhydride (cis-1,2,3,4-CHDA) was synthesized. It was found that under such conditions as heating or boiling in acetic anhydride, cis-1,2,3,4-CHDA could be converted to its trans-isomer. The process of thermal isomerization was monitored by H-1 NMR spectra and the mechanism of conversion was proposed. Their absolute structures of cis- and trans-1,2,3,4-CHDAs were elucidated by single crystal X-ray diffraction. The polycondensations of cis- and trans-1,2,3,4-CHDAs with aromatic diamines such as 4,4'-oxydianiline (ODA), 4,4'-methylenedianiline (MDA), 4,4'-diamino-3,3'-dimethyldiphenylmethane (DMMDA), 4,4'-bis(4-aminophenoxy)benzene (TPEQ), 2,2-bis[4-(4-aminophenoxy)phenyl] propane (BAPP) were studied. It is easy to obtain higher molecular weight polyimides from trans-1,2,3,4-CHDA using conventional one-step or two-step methods. However, higher molecular weight polyimides derived from cis-1,2,3,4-CHDA could not be prepared by the usual methods (solid content ca. 10%) owing to the trend of forming cyclic oligomers.

Syntheses and properties of polyimides derived from diamines containing 2,5-disubstituted pyridine group

A Series of novel homo- and copolyimides containing pyridine units were prepared from the heteroaromatic diamines, 2,5-bis (4-aminophenyl) pyridine and 2-(4aminophenyl)-5-aminopyridine, with pyromelltic dianhydride (PMDA), and 3,3',4,4'-biphenyl tertracarboxylic dianhydride (BPDA) via a conventional two-step thermal imidizaton method. The poly(amic acid) precursors have inherent viscosities of 1.60-9.64 dL/g (c = 0.5 g/dL in DMAC, 30 degrees C) and all of them can be cast and thermally converted into flexible and tough polyimide films. All of the polyimides show excellent thermal stability and mechanical properties. The polyimides have 10% weight loss temperature in the range of 548-598 degrees C in air. The glass transition temperatures of the PMDA-based samples are in the range of 395-438 degrees C, while the BPDA-based polyimides show two glass transition temperatures (T(g)1 and T(g)2), ranging from 268 to 353 degrees C and from 395 to 418 degrees C, respectively. The flexible films possess tensile modulus in the range of 3.42-6.39 GPa, strength in the range of 112-363 MPa and an elongation at break in the range of 1.2-69%. The strong reflection peaks in the wide-angle X-ray diffraction patterns indicate that the polyimides have a high packing density and crystallinity.

Synthetic studies on optically active Schiff-base ligands derived from condensation of 2-hydroxyacetophenone and chiral diamines

Three optically active Schiff-base ligands have been prepared by condensation of 2-hydroxyacetophenone with (IR,2R)-(-)-1,2-diaminocyclohexane, (1S,2S)-(-)1,2-diphenylethylenediamine or R-(+)-2,2'-diamino-1,1'-binaphthalene, respectively. The products have been characterized by their IR, H-1- and C-13-NMR spectra.

Simple and Encapsulated Transition Metal Complexes of Schiff Bases Derived from Quinoxaline-2-Carboxaldehyde and Diamines: Biological and Catalytic Activity Studies

This thesis is mainly concerned with the synthesis and characterisation of new simple and zeolite encapsulated transition metal (manganese(II),nickel(II),and copper(II)complexes of quinoxaline based double Schiff base ligands.Theses ligands are N,N'-bis(quinoxaline-2-carboxalidene)hydrazine,N,N'-bis(quinoxaline-2-carboxalidene)-1,2-diaminoethane,N,N'-bis(quinoxaline-2-carboxalidene)-1,3-diamonopropane,N,N'-bis(quinoxaline-2-carboxalidene)-1,4-diaminobutane,N,N'-bis(quinoxaline-2-carboxalidene)-1,2-diaminocyclohexane and N,N'-bis(quinoxaline-2-carboxalidene)-1,2-diaminobenzene.The Schiff base ligands have been characterised by spectral and single crystal XRD studies.Theses ligands provide great structural diversity during complexation.Mn(II) and Ni(II) form octahedral with these Schiff bases,whereas Cu(II) forms both octahedral and tetrahedral complexes.Studies on the biological and Catalytic activity of the copper(ll) complexes are also presented in this thesis.

Facile bisurethane supramolecular polymers containing flexible alicyclic receptor units

This paper details the synthesis, characterisation and physical analyses of a series of hydrogen bonded urethane supramolecular polymer systems that are created by a facile one-step synthesis from inexpensive and commercially available starting materials. We report the synthesis and characterisation of a series of low molecular weight bisurethanes (<650 a.m.u.) that exhibit physical properties in the bulk that are characteristic of polyurethane materials possessing far higher molecular weight. The physical characteristics of these low molecular weight bisurethanes were investigated by using temperature-dependent rheological analysis and viscometry and the nature in which these compounds assembled was assessed using IR and NMR spectroscopies. These studies reveal that these simple bisurethanes self-assemble via hydrogen bonding interactions.

Two New Supramolecular Assemblies Obtained by Reaction Between Saccharin and Long-chain Diamines

The crystal Structures of heptamethylenediammonium bis(saccharinate) monohydrate, [H(3)N-(CH(2))(7)-NH(3)](sac)(2)center dot H(2)O (1) 0 (1) and octamethylenediammonium bis(saccharinate) hemihydrate, [H(3)N-(CH(2))(8)-NH(3)](sac)(2)center dot 0.5H(2)O (2), were determined-by single-crystal X-ray diffraction methods. Compound I crystallizes in the triclinic space group P (1) over bar with 2 molecules per unit cell, and 2 in the monoclinic space group P2(1)/a with Z = 4. The saccharinate moiety is planar in both compounds presenting bonding characteristics comparable to those found in other saccharinate salts. The ionic crystals are further stabilized by an extensive H-bonding network, which links the anions and cations into an infinite three-dimensional Supramolecular assembly. The FTIR spectra of the adducts are briefly discussed in comparison with those of the constituent Molecules.