Synthesis of isomeric bis(amine anhydride)s for novel poly(amine imide)s by Pd-catalyzed amination of 4-chlorophthalic anhydride

Two novel bis(amine anhydride) monomers, N,N'-bis(3,4-dicarboxyphenyl)-1,4-phenylenediamine dianhydride I and N,/N'-bis(3,4-dicarboxyphenyl)-1,3-phenylenediamine dianhydride 11, were prepared via palladium-catalyzed amination reaction of 4-chloro-N-methylphthaliniide with 1,4-phenylenediamine or 1,3-phenylenediamine, followed by alkaline hydrolysis of the intermediate bis(amine imide)s and subsequent dehydration of the resulting tetraacids. A series of new poly(amine imide)s were prepared from the synthesized dianhydride monomers with various diamines in NMP via conventional two-step method.

The synthesis of a 1,1'-bi-2-naphthol-based bis(ether anhydride) and aromatic polyimides derived therefrom

2,2'-Bis(3,4-dicarboxyphenoxy)-1,1'-binaphthyl dianhydride was used as a new monomer with various aromatic diamines to obtain polyimides by the usual two-step method. The bis(ether anhydride) was prepared by a nucleophilic substitution of I,1'-bi-2-naphthol with N-phenyl-4-chlorophthalimide, N-methyl-4-nitrophthalimide or 4-nitrophthalonitrile in aprotic polar solvent, and subsequent hydrolysis of the resulting bis(ether imide)s or bis(ether dinitrile), and then dehydration of the corresponding tetracarboxylic acid to afford the dianhydride. Most of the obtained polyimides were soluble in chloroform, pyridine, DMF, etc. The polyimide prepared from p-phenylene diamine was partial crystalline, whereas the others showed amorphous patterns in a WAXD study. These polymers have glass transition temperatures between 255-294 degrees C and 5% weight loss temperatures in the range of 502-541 degrees C in nitrogen and 473-537 degrees C in air. (C) 1997 Elsevier Science Ltd.

Synthesis of bis(amine anhydride)s for novel high T(g)s and organosoluble poly(amine imide)s by palladium-catalyzed amination of 4-chlorophthalide anhydride

Two novel bis(amine anhydride)s, NN-bis(3,4-dicarboxyphenyl)aniline dianhydride (I) and N,N-bis(3,4-dicarboxyphenyl)-p-tert-butylaniline (II), were synthesized from the palladium-catalyzed amination reaction of N-methyl-protected 4-chlorophthalic anhydride with arylamines, followed by alkaline hydrolysis of the intermediate bis(amine-phthalimide)s and subsequent dehydration of the resulting tetraacids. The X-ray structures of anhydride I and II were determined. The obtained dianhydride monomers were reacted with various aromatic diamines to produce a series of novel polyimides. Because of the incorporation of bulky, propeller-shaped triphenylamine units along the polymer backbone, all polyimides exhibited good solubility in many aprotic solvents while maintaining their high thermal properties. These polymers had glass transition temperatures in the range of 298-408 degrees C. Thermogravimetric analysis showed that all polymers were stable, with 10% weight loss recorded above 525 degrees C in nitrogen.The tough polymer films, obtained by casting from solution, had tensile strength, elongation at break, and tensile modulus values in the range of 95-164 MPa, 8.8-15.7%, and 1.3-2.2 GPa, respectively.

Phase transition and transition kinetics of a thermotropic poly(amide-imide) derived from 70% pyromellitic dianhydride, 30% terephthaloyl chloride, and 1,3-bis[4-(4 '-aminophenoxy)cumyl]benzene

The phase transition and transition kinetics of a liquid crystalline copoly(amide-imide) (PAI37), which was synthesized from 70 mol% pyromellitic dianhydride, 30 mol% terephthaloyl chloride, and 1,3-bis[4-(4'-aminophenoxy)cumyl]benzene, was characterized by differential scanning calorimetry, polarized light microscopy, X-ray diffraction, and rheology. PAI37 exhibits a glass transition temperature at 182 degreesC followed by multiple phase transitions. The crystalline phase starts to melt at similar to 220 degreesC and forms smectic C (S-C) phase. The Sc phase transforms into smectic A (S-A) phase when the temperature is above 237 degreesC. The S-C to S-A transition spans a broad temperature range in which the S-A phase vanishes and forms isotropic melt. The WARD fiber pattern of PAI37 pulled from the anisotropic melt revealed an anomalous chain orientation, which was characterized by its layer normal perpendicular to the fiber direction. The transition kinetics for the mesophase and crystalline phase formation was also studied.

Synthesis and properties of novel fluorinated poly(phenylene-co-imide)s

A new class of high-performance materials, fluorinated poly(phenylene-co-imide)s, were prepared by Ni(0)-catalytic coupling of 2,5-dichlorobenzophenone with fluorinated dichlorophthalimide. The synthesized copolymers have high molecular weights ((M) over bar (W)= 5.74 x 10(4)-17.3 x 10(4) g center dot mol(-1)), and a combination of desirable properties such as high solubility in common organic solvent, film-forming ability, and excellent mechanical properties. The glass transition temperature (T(g)s) of the copolymers was readily tuned to be between 219 and 354 degrees C via systematic variation of the ratio of the two comonomers. The tough polymer films, obtained by casting from solution, had tensile strength, elongation at break, and tensile modulus values in the range of 66.7-266 MPa, 2.7-13.5%, and 3.13-4.09 GPa, respectively. The oxygen permeability coefficients (P-O2) and permeability selectivity of oxygen to nitrogen (P-O2/P-N2) of these copolymer membranes were in the range of 0.78-3.01 barrer [1 barrer = 10(-10) cm(3) (STP) cm/(cm(2) center dot s center dot cmHg)] and 5.09-6.2 5, respectively. Consequently, these materials have shown promise as engineering plastics and gas-separation membrane materials.

Synthesis and chirooptical properties of optically active poly(ester imide)s based on axially asymmetric 1,1 '-binaphthyls

A series of optically active poly(ester imide)s (PEsI's) has been synthesized by the polycondensation reactions of new axially asymmetric dianhydrides, that is, (R)-2,2'-bis(3,4-dicarboxybenzoyloxy)-1,1'-binaphthyl dianhydride and (S)-2,2'-bis(3,4-dicarboxybenzoyloxy)-1,1'-binaphthyl dianhydride, and various diamines with aromatic, semiaromatic, and aliphatic structures. The polymers have inherent viscosities of 0.45-0.70 dL/g, very good solubility in common organic solvents, glass-transition temperatures of 124-290 degreesC, and good thermal stability. Wide-angle X-ray crystallography of these polymers shows no crystal diffraction. In comparison with model compounds, an enhanced optical rotatory power has been observed for the repeat unit of optically active PEsI's based on aromatic diamines, and it has been attributed to a collaborative asymmetric perturbation of chiral 1,1'-binaphthyls along the rigid backbones.

Microwave-assisted synthesis of high-molecular-weight poly(ether imide)s by phase-transfer catalysis

A facile and rapid polycondensation reaction of disodium bisphenol A with bis(chlorophthalimide)s was preformed with a domestic microwave oven in o-dichlorobenzene by phase-transfer catalysis. The polymerization reactions, in comparison with conventional heating polycondensation, proceeded rapidly and were completed within 25 min. The polymerizations gave the corresponding poly(ether imide)s with inherent viscosities of 0.55-0.92 dL g(-1). The effects of various factors on the polymerization, such as the amount of the catalyst, the reaction time, and the microwave power were studied. The properties of the polymers were briefly characterized.

Copolymerization of dichlorodiphenylsulfone with bis(chlorophthalimide) catalyzed by NiBr2/PPh3/Zn

A new high-performance material, poly(sulfone-imide) was prepared by Ni(0)-catalyzed coupling of aromatic dichlorides containing imide structure and 4,4'-dichlorodiphenylsulfone. The copolymers were produced with high yield and moderate to high inherent viscosities of 0.52-1.13 dL/g. Wide-angle X-ray diffractograms revealed that the polymers were amorphous. Most of the polymers exhibited good solubility and could be readily dissolved in various solvents such as N-methyl-2-pyrrolidinone(NMP) and N,N-dimethylacetamide (DMAc). These polysulfone-imides had glass-transition temperatures between 317 and 345 degreesC and 10% weight loss temperatures in the range of 450476 degreesC in nitrogen atmosphere. The tough polymer films, obtained by casting from cresol solution, had a tensile strength range of 21 158 MPa and a tensile modulus range of 2.1-3.3 GPa.

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.

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.

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.

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.

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.

Optically active poly(amide-imide)s containing axially dissymmetric 1,1 '-binaphthyl moieties

Novel optically active aromatic poly(amide-imide)s (PAIs) were prepared from newly synthesized 2,2'-bis(3,4-dicarboxybenzamido)-1,1'-binaphyl dianhydride ((+/-)-, (S)-, and (R)-BNDADA). PAIs based on dianhydride monomers with different ee % were investigated with respect to their structures and chiroptical properties. These polymers were highly soluble in polar aprotic solvents such as N,N-dimethylacetamide, N-methyl-2-pyrrolidone, pyridine, etc., and showed high glas s transition temperatures of 287-290 degrees C and 5% weight loss temperatures of 450-465 degrees C in nitrogen. Optically active PAIs exhibited high specific rotations, excellent optical stabilities, and a dependence of optical activities on temperature. Investigations on chiroptical properties indicated that chiral conformation was possessed by optically active PAIs. (C) 1999 John Wiley & Sons, Inc.