Synthesis and characterization of new carbazole/fluorene-based derivatives for blue-light-emitting devices

2,7-Bis(9-ethylcarbazol-3-yl)-9,9-di(2-ethylhexyl)fluorene and a segmented copolymer composed of the same chromophores alternated with hexamethylene fragments were synthesized. The obtained materials possess good solubility in common organic solvents, high thermal stability with 1% weight loss temperature of 350-370 degrees C, and suitable glass transition temperatures. Both derivatives show blue fluorescence in dilute solutions as well as in solid state, demonstrating that excimers are not formed in the thin films. The fluorescence spectra of the materials do not show any peaks in the long-wavelength region even after annealing at 200 degrees C in air. An organic LED with the configuration of ITO/copolymer/Al generates blue electroluminescence with the maximum peak at 416 nm, rather low turn-on voltage (4.0 V), and brightness of about 400 cd/m(2). The heterostructure device based on model derivative emitted stable blue light with low operation voltage (100 cd/m(2) at similar to 11 V) and demonstrated luminescence efficiency of 0.8 cd/A.

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.

One-pot synthesis of polyetherimides from bis(chlorophthalimide) and dichlorodiphenylsulfone in diphenylsulfone

Polyetherimides and copolymers have been synthesized in one pot from bis(chlorophthalimide), dichlorodiphenylsulfone, and bisphenolate using diphenylsulfone as the solvent. The inherent viscosities of the obtained polyimides are in the range of 0.32-0.72 dL/g, and the structures of polyimides were confirmed by IR and elemental analyses. All of the polyimides have good solubility in common organic solvents. The 5% weight-loss temperatures of the polyimides were 429-507 C in air. The glass transition temperatures (T3) of 4,4'-(9-fluorenylidene) diphenol-based polyimides are in the range of 253-268 degrees C. The Tg of bisphenol A-based polyimides is in the range of 198204 degrees C, while the T-g change inconspicuously when the ratios of diphenylsulfone increase. The wide-angle X-ray diffraction showed that all polyimides prepared are amorphous.

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.

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.

Synthesis and characterization of hyperbranched aromatic poly(ether imide)s

The four AB(2) monomers, N-[3- or 4-bis(4-hydroxyphenyl)toluoyl]-4-chlorophthalimide and N-{3- or 4-[1,1-bis(4-hydroxyphenyl)]ethylphenyl}-4-chlorophthalimides, were prepared and used for synthesis of hyperbranched poly(ether imide)s bearing hydroxyl end groups. These hyperbranched poly(ether imide)s had moderate molecular weights with broad distributions and showed glass-transition temperatures (Tgs) between 177 and 230 degreesC. The thermogravimetric analytic measurement revealed the decomposition temperature at 5% weight-loss temperatures (T-d(5%)) ranging from 240 to 281 degreesC. Analysis using H-1 NMR spectroscopy revealed the four types of hyperbranched poly(ether imide)s to have similar degrees of branching (ca. 60%). These polymers were modified by acylation or nucleophilic substitution reaction at the hydroxyl end groups. The conversion effectiveness depended on the type of modification reaction, modifier, and reaction conditions. The thermal stability and solubility of hyperbranched poly(ether imide)s were improved by the modification of the end groups.

Synthesis and characterization of hyperbranched aromatic poly(ester-imide)s

The synthesis and characterization of hyperbranched aromatic poly(ester-imide)s are described. A variety of AB(2) monomers, N-[3- or 4-bis(4-acetoxyphenyl)toluoyl]-4-carboxyl-phthalimide and N-{3- or 4-[1,1-bis(4-acetooxyphenyl)]ethylphenyl}-4-carboxy phthalimides were prepared starting from condensation of nitrobenzaldehydes or nitroacetophenones with phenol and used for synthesis of hyperbranched poly(ester-imide)s containing terminal acetyl groups by transesterification reaction. These hyperbranched poly(ester-imide)s were produced with weight-average molecular weight of up to 6.87 g/mol. Analysis of H-1 NMR and C-13 NMR spectroscopy revealed the structure of the four hyperbranched poly(ester-imide)s. These hyperbranched poly(ester-imide)s exhibited excellent solubility in a variety of solvents such as N,N-dimethylacetamide, dimethyl sulfoxide, and tetrahydrofuran and showed glass-transition temperatures between 217 and 255 degreesC. The thermogravimetric analytic measurement revealed the decomposition temperature at 10% weight-loss temperature (T-d(10)) ranging from 365 to 416 degreesC in nitrogen.

Preparation and characterization of nanocrystalline CeO2 by precipitation method

CeO2 nanocrystalline particulates with different sizes were prepared by precipitation method using ethanol as dispersive and protective reagent. XRD spectra show that the synthesized CeO2 has cubic crystalline structure of space group O-H(5)-F-M3M, when calcination temperature is in the range of 250 similar to 800 degreesC. TEM images reveal that CeO2 particles are spherical in shape. The average size of the particles increases with the increase of calcination temperature. Thermogravimetric analysis indicates that the weight loss of precursor mainly depends on the calcination temperature, and little depends on the calcination time. Measurements of CeO2 relative density show that the relative density of CeO2 nanocrystalline powders increases with increasing CeO2 particle size.

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.

Thermal degradation kinetics of poly(propylene carbonate) obtained from the copolymerization of carbon dioxide and propylene oxide

The kinetics of the thermal degradation of poly(propylene carbonate) (PPC) were investigated with different kinetic methods with data from thermogravimetric analysis under dynamic conditions. The apparent activation energies obtained with different integral methods (Ozawa-Flynn-Wall and Coats-Redfern) were consistent with the values obtained with the Kinssinger method (99.93 kJ/mol). The solid-state decomposition process was a sigmoidal A(3) type in terms of the Coats-Redfern and Phadnis-Deshpande results. The influence of the heating rate on the thermal decomposition temperature was also studied. The derivative thermogravimetry curves of PPC confirmed only one weight-loss step.

Photochromic behavior and luminescent properties of novel hybrid organic-inorganic film doped with Preyssler's heteropoly acid H-12[EuP5W30O110] and polyvinylpyrrolidone

A novel hybrid photochromic composite film composed of Preyssler's heteropoly acid H-12[EuP5W30O110] (EuP5W30) and polyvinylpyrrolidone (PVP) was prepared by dip-coating method. Atomic force microscopy (AFM) was used to investigate the surface topography. The change of characteristic peak in the infrared spectra (IR) was investigated. The TG curve showed three steps of weight loss and approximately revealed the composition of the hybrid film. Ultraviolet-visible adsorption spectra (UV-VIS) and electron resonance spectrum (ESR) were used to investigate the photochromic behavior and mechanism of hybrid film. The photoluminescent behavior of the film at room temperature was investigated to show the characteristic Eu3+ emission pattern of D-5(o)-F-7(J). The occurrence of photoluminescent activity confirms the potential for creating luminescent thin film with polyoxometalates (POMs).

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.

Synthesis and characterization of network liquid crystal elastomers and thermosets

A new series of network liquid crystal polymers were synthesized by graft copolymerization of the difunctional mesogenic monomer 4-allyloxy-benzoyloxy-4'-allyloxybiphenyl (M) upon polymethylhydrosiloxane (PMHS). Monomer M acted not only as a mesogenic unit but also as a crosslinker for the network polymers. The chemical structures of the polymers were confirmed by IR spectroscopy. DSC, TGA, and X-ray scattering were used to measure their thermal properties and mesogenic properties. The glass transition temperature (T-g) of these network liquid crystal polymers was increased when the monomer was increased, and T-d (temperature of 5% weight loss) at first went up and reached a maximum at P, then went down. The slightly crosslinked polymers (P, P,) show rubber-like elasticity, so it was called liquid-crystal elastomer. Network polymers will lose elasticity property with a highly crosslinked degree, and turn into thermosetting polymers (P-4, P-5). All polymers exhibited a smectic texture by X-ray scattering.

Polyimides from isomeric biphenyltetracarboxylic dianhydrides and the effects of chemical structure on solubility

A series of homopolyimides and copolyimides was synthesized by the solution condensation of biphenyltetracarboxylic dianhydride (BPDA) isomers and various diamines followed by chemical imidization. These polyimides had intermediate to high molecular weights with inherent viscosities of 0.34-1.01 dL/g for homopolyimides and 0.48-1.02 dL/g for copolyimides. Thermogravimetric analysis indicated that the aromatic polyimides were stable up to 500degreesC, and the 5% weight loss temperatures were recorded in the range of 506-597degreesC in an air atmosphere and in the range of 517-601degreesC in a nitrogen atmosphere, depending on the diamines used. The glass transition temperatures of aromatic homopolyimides were above 271degreesC, while the glass transition temperatures of the copolyimides increased with an increase in the 2, 2', 3, 3'-BPDA-component. The effects of the chemical structure of the polymer chain on the solubility were investigated. It was found that the solubility of BPDA-based polyimides could be improved by the introduction of flexible units, nonlinear and non-coplanar units, and copolymerization. The polyimides with nonlinear and non-coplanar units derived from 2, 2', 3, 3'-BPDA appeared to have prominently enhanced solubility in polar aprotic solvents and polychlorocarbons when compared with the homopolyimide derived from 3, 3', 4, 4'-BPDA.

Aromatic poly(ester imide)s and poly(amide imide)s having 1,1 '-binaphthyl-2,2 '-diyls in the main chain

Full Paper: Two new 1,1'-binaphthyl-2,2'-diyl-based dianhydrides, i.e., 2,2'-bis(3,4-dicarboxybenzamido)-1,1'-binaphthyl dianhydride (BNDADA) and 2,2'-bis(3,4-dicarboxybenzoyloxy)-1,1'-binaphthyl dianhydride (BNDEDA), were synthesized and polymerized with various aromatic diamines to afford polyimides through the traditional two-step method. The polyimides with inherent viscosities ranging from 0.27 to 0.70 dl . g(-1) showed excellent solubilities in polar solvents such as DMAc, DMSO and NMP etc., except of the poly(ester imide) prepared from BNDEDA and benzidine. Poly(ester imide)s based on BNDEDA can also be readily dissolved in weakly polar solvents such as THF, CH2Cl2 and CHCl3. The glass transition temperatures of these polyimides are in the range of 210-310 degrees C; the 5% weight loss temperatures are in the range of 390-465 degrees C in nitrogen and 384-447 degrees c in air. These polymers from light yellow, tough films that were transparent above 365 nm. The effects of different flexible units attached in the 2- and 2'-positions, i.e., amide, ester and ether, on the properties of the polyimides obtained are discussed.