RAPID SYNTHESIS OF NOVEL OPTICALLY ACTIVE POLY（AMIDE-IMIDE）S DERIVED FROM N,N′-（PYROMELLITOYL）-BIS-L-ALANINE DIACID CHLORIDE AND HYDANTOIN DERIVATIVES UNDER MICROWAVE IRRADIATION

Eight novel poly(amide-imide)s were synthesized under microwave irradiation by using a domestic microwaveoven from the polycondensation reactions of N,N′-(pyromellitoyl)-bis-L-alanine diacid chloride (1) with eight different derivatives of hydantoin compounds (2a-h) in the presence of a small amount of a polar organic medium such as o-cresol. The polycondensation proceeded rapidly, compared with the conventional solution polycondensation and was completed within 8-10min, producing a series of new poly(amide-imide)s (3a-h) with inherent viscosities about 0.35-0.68dL/g in high yields. The obtained PAIs (3a-h) were fully characterized by means of FT-IR spectroscopy, elemental analyses, inherent viscosity (ηinh), solubility and specific rotation measurements. All of the resulting polymers show optical rotation and are optically active. Thermal properties of the poly(amide-imide)s were investigated by using thermal gravimetric analysis(TGA).     

POLYMERIZATION OF N,N′-（PYROMELLITOYL）-BIS-L-LEUCINE DIACID CHLORIDE WITH HYDANTOIN DERIVATIVES BY MICROWAVE IRRADIATION

Facile and rapid polycondensation reactions of N,N′-(pyromellitoyl)-bis-L-leucine diacid chloride 1 with eight different derivatives of hydantoin compounds 2a-h were developed by using a domestic microwave oven in the presence of a small amount of polar organic medium such as o-cresol. The polycondensation reactions proceeded rapidly, compared with the conventional solution polycondensation, and was completed within 7-10 min, producing a series of novel optically active poly(amide-imide)s 3a-h with high yield and inherent viscosity of 0.35-0.65 dL/g. All of the above polymers were fully characterized by FT-IR, elemental analyses, inherent viscosity (ηinh), solubility test and specific rotation. Some structural characterization and physical properties of these optically active poly(amide-imide)s are reported.     

POLYMERIZATION OF N,N′-(PYROMELLITOYL)-BIS-L-LEUCINE DIACID CHLORIDE WITH HYDANTOIN DERIVATIVES BY MICROWAVE IRRADIATION

Facile and rapid polycondensation reactions of N,N′-(pyromellitoyl)-bis-L-leucine diacid chloride 1 with eight different derivatives of hydantoin compounds 2a-h were developed by using a domestic microwave oven in the presence ora small amount of polar organic medium such as o-cresol. The polycondensation reactions proceeded rapidly, compared with the conventional solution polycondensation, and was completed within 7-10 min, producing a series of novel optically active poly(amide-imide)s 3a-h with high yield and inherent viscosity of 0.35-0.65 dL/g. All of the above polymers were fully characterized by FT-IR, elemental analyses, inherent viscosity (ηiaa), solubility test and specific rotation. Some structural characterization and physical properties of these optically active poly(amide-imide)s are reported.     

New poly(amide-lmide)s syntheses. XV. Preparation and properties of poly(amide-imide)s derived from 9, 9-bis[4-(4-aminophenoxy) phenyl]fluorene and various bis(trimellitimide)s

Fifteen bis(phenoxy) fluorene-containing poly(amide-imide)s III were synthesized by the direct polycondensation of 9,9-bis[4-(4-aminophenoxy)phenyl]fluorene (BAPPF) with var-ious aromatic bis(trimellitimide)s II in N-methyl-2-pyrrolidone (NMP) using triphenyl phosphite and pyridine as condensing agents. Poly(amide-imide)s III having inherent vis-cosities up to 1.45 dL/g were obtained in quantitative yields. Most of the resulting polymers showed an amorphous nature and were readily soluble in polar solvents such as NMP and N,N-dimethylacetamide. All the soluble poly(amide-imide)s afforded transparent, flexible, and tough films. The glass transition temperatures of these polymers were in the range of 263–315°C and the 10% weight loss temperatures were above 510°C in nitrogen. Some properties of poly(amide-imide)s III were compared with those of the corresponding isomeric poly(amide-imide)s III ′ prepared from 9,9-[4-(4-trimellitimidophenoxy)phenyl]fluorene and various aromatic diamines. © 1995 John Wiley & Sons, Inc.     

New poly(amide-imide)s syntheses. XVII. Preparation and properties of poly(amide-imide)s derived from 3,3-Bis[4-(4-aminophenoxy)phenyl]phthalimidine and various bis(trimellitimide)s

A series of novel bis(phenoxy)phthalimidine-containing poly(amide-imide)s III were synthesized by the direct polycondensation of 3,3-bis[4-(4-aminophenoxy)phenyl]phthalimidine (BAPP) with various aromatic bis(trimellitimide)s in N-methyl-2-pyrrolidone (NMP) using triphenyl phosphite and pyridine as condensing agents. Poly(amide-imide)s III , having inherent viscosities up to 1.36 dL/g, were obtained in quantitative yields. All resulting polymers showed an amorphous nature and were readily soluble in polar solvents such as NMP and N,N-dimethylacetamide. All the soluble poly(amide-imide)s afforded transparent, flexible, and tough films. The glass transition temperatures of these polymers were in the range of 267–322°C and the 10% weight loss temperatures were above 490°C in nitrogen. Some properties of poly(amide-imide)s III were compared with those of the corresponding isomeric poly(amide-imide)s III′ prepared from 3,3-[4-(4-trimellitimidophenoxy)phenyl]-phthalimidine and various aromatic diamines. © 1996 John Wiley & Sons, Inc.     

New optically active poly（amide-imide）s derived from N, N′-（4,4-diphthaloyl）-bis-L-leucine and hydantoin derivatives： Synthesis and properties

Six new optically active poly(amide-imide)s(5a-f) were synthesized through the direct polycondensation reaction of N,N'-(4,4'- diphthaloyl)-bis-L-leucine(3) with six hydantoin derivatives(4a-f).Triphenyl phosphite(TPP)/pyridine in the presence of calcium chloride(CaCl_2) and N-methyl-2-pyrrolidone(NMP) were successfully applied for direct polycondensation.The polycondensation reactions produce a series of new poly(amide-imide)s(5a-f) in high yields,and inherent viscosity between 0.42 and 0.55 dL/g.The re...     

Synthesis and characterization of optically active poly(amide-imide)s containing photosensitive chalcone units in the main chain

<正>A series of new optically active poly(amide-imide)s were synthesized by direct polycondensation reaction of 4,4'-diaminochalcone with several N-trimellitylimido-L-amino acids using a tosyl chloride(TsCl),pyridine(Py) and dimethylformamide(DMF) system as condensing agent.The resulting thermally stable poly(amide-imide)s were obtained in good to high yields and inherent viscosities ranging between 0.35 dL/g and 0.58 dL/g and were characterized with FTIR, ~1H-NMR,CHN,Ultraviolet,TGA and DTG techniques.     

New poly(amide-imide)s syntheses. II. Soluble poly(amide-imide)s derived from 2,5-bis(4-aminophenyl)-3,4-diphenylthiophene and various N-(ω-carboxyalkyl)-trimellitimides,N-(carboxyphenyl)trimellitimides,or N,N″-bis(ω-carboxyalkyl)pyromellitimides

Various dicarboxylic acids with preformed imide rings were readily obtained by the condensation of ω-amino acids and aminobenzoic acids with trimellitic anhydride, and omega;-amino acids with pyromellitic dianhydride. New tetraphenylthiophene-containing poly(amide-imide)s having inherent viscosities of 0.58-1.54 dL/g were prepared by the direct polycondensation reaction of 2,5-bis(4-aminophenyl)-3,4-diphenylthiophene with the imide-containing dicarboxylic acids using triphenyl phosphite and pyridine as condensing agents. These polymers were amorphous and readily soluble in a variety of solvents such as dimethylacetamide (DMAc), dimethylformamide (DMF), and N-methyl–2-pyrrolidone (NMP), and could be easily solution cast into transparent, flexible, and tough films. Most of the poly(amide-imide)s showed clear glass transition on the heating traces of differential scanning calorimetry (DSC) in the range of 146–244°C. Almost all the poly(amide-imide)s exhibited no appreciable decomposition below 400°C, with 10% weight loss being recorded above 420°C in nitrogen. © 1992 John Wiley & Sons, Inc.     

Synthesis and characterization of new aromatic poly(amide-imide)s derived from bis(3-trimellitimidophenyl) phenyl phosphine oxide and various aromatic diamines

New aromatic poly(amide-imide)s with high inherent viscosities were prepared by direct polycondensation reaction of diimide-diacid (I) and aromatic diamines using triphenyl phosphite in N-methyl-2-pyrrolidone (NMP)/pyridine solution containing dissolved CaCl₂. The bis(3-trimellitimidophenyl) phenyl phosphine oxide (I) was readily obtained by the condensation reaction of bis(3-aminophenyl) phenyl phosphine oxide (BAPPO) with trimellitic anhydride. The resulting poly(amide-imide)s showed high thermostability. Their decomposition temperatures at 10% weight loss in nitrogen atmosphere were above 532 °C and the anaerobic char yield at 800 °C ranged from 56% to 74%. Almost all the poly(amide-imide)s showed high glass transition temperature above 233 °C by differential scanning calorimetry (DSC) measurements. These polymers were readily soluble in various organic solvents and by their casting into transparent, tough and flexible films can be easily achieved.     

Synthesis of aromatic poly(amide-imide)s from novel diimide-diacid (DIDA) containing sulphone and bulky pendant groups by direct polycondensation with various diamines

A novel diimide-diacid (DIDA) monomer, 4-{4-[(4-methyl phenyl) sulphonyl]}-1,3-bis-trimellitoimido benzene containing sulphone and bulky pendant groups was successfully synthesized and used to synthesize a series of wholly aromatic poly(amide-imide)s (PAIs) by direct polycondensation method. The direct polycondensation of newly synthesized DIDA with different diamines was carried out via Yamazaki’s phosphorylation method using triphenyl phosphite and pyridine system. The resulting poly(amide-imide)s were obtained in quantitative yields with inherent viscosities 0.36-0.47 dl/g in DMAc at 30 ± 0.1 °C. The poly(amide-imide)s were amorphous and were readily soluble in various solvents such as N-methyl-2-pyrrolidinone (NMP), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), and pyridine. Tough and flexible films were obtained by casting their DMAc solution. According to thermogravimetric analysis, the polymers were fairly stable up to temperature around 396 °C, and 10% weight losses in the temperature range of 476-511 °C that showed good thermal stabilities of these polymers.     

New poly(amide-imide) syntheses. V. Preparation and properties of poly(amide-imide)s based on the diimide—diacid condensed from 2,2-bis[4-(4-aminophenoxy)phenyl]propane and trimellitic anhydride

A dicarboxylic acid ( 1 ) bearing two pre-formed imide rings, was prepared from the condensation of 2,2-bis[4-(4-aminophenoxy)phenyl]propane and trimellitic anhydride. A new family of poly(amide-imide)s having inherent viscosities of 0.53–1.68 dL/g was prepared by the triphenyl phosphite activated polycondensation from the diimide—diacid I with various aromatic diamines in a medium consisting of N-methyl-2-pyrolidone (NMP), pyridine, and calcium chloride. Most of the resulting polymers showed an amorphous nature and were readily soluble in polar solvents such as NMP and N,N-dimethylacetamide. All the soluble poly(amide-imide)s afforded transparent, flexible, and tough films. The glass transition temperatures of these poly(amide-imide)s were in the range of 237–293°C and the 10% weight loss temperatures were above 508°C in nitrogen. © 1993 John Wiley & Sons, Inc.     

Synthesis and properties of poly(amide-imide)s derived from trimellitic anhydride, ω-amino acids,and aromatic diamines

Seven imidodicarboxylic acids II -1 to 5, II -10, and II -11 were prepared from trimellitic anhydride and ω-amino acids, such as glycine, β-alanine, 4-aminobutyric acid, 5-aminopentanoic acid, 6-aminohexanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. Several aliphatic-aromatic poly(amide-imide)s were prepared by triphenyl phosphite promoted polycondensation reaction from the combination of 3-(4-carboxyphthalimido)propionic acid ( II -2) or 6-(4-carboxyphtalimido)hexanoic acid ( II -5) with various aromatic diamines and of all the imidodiacids with p-phenylenediamine or 4,4′-oxydianiline. All poly(amide-imide)s were characterized by inherent viscosity, gel permeation chromatography (GPC) measurements, solubility, tensile test, wide-angle X-ray scatting patterns, differential scanning calorimetry (DSC) measurements, and thermogravimetric (TGA) analyses. Effects of structural changes such as polymethylene length and diamine moieties on the properties of poly(amide-imide)s were studied. © 1994 John Wiley & Sons, Inc.     

New poly (amide-imide) syntheses. IX. Preparation and properties of poly(amide-imide)s derived from 2,7-bis (4-aminophenoxy) naphthalene and various bis (trimellitimide)s

Eleven bis(phenoxy) naphthalene-containing poly(amide-imide)s IIIa–k were synthesized by the direct polycondensation of 2,7-bis (4-aminophenoxy) naphthalene (DAPON) with various aromatic bis (trimellitimide)s IIa–k in N-methyl-2-pyrrolidone (NMP) using triphenyl phosphite and pyridine as condensing agents. Poly (amide-imide)s IIIa–k having inherent viscosities of 0.70–1.12 dL/g were obtained in quantitative yields. The polymers containing p-phenylene or bis(phenoxy) benzene units exhibited crystalline x-ray diffraction patterns. Most of the polymers were readily soluble in various solvents such as NMP, N, N-dimethylacetamide, dimethyl sulfoxide, m-cresol, o-chlorophenol, and pyridine, and gave transparent, and flexible films cast from DMAc solutions. Cast films showed obvious yield points in the stress-strain curves and had strength at break up to 87 MPa, elongation to break up to 11%, and initial modulus up to 2.10 GPa. These poly(amide-imide)s had glass transition temperatures in the range of 255–321°C, and the 10% weight loss temperatures were recorded in the range of 529–586°C in nitrogen. The properties of poly(amideimide)s IIIa–k were compared with those of the corresponding isomeric poly (amide-imide)s III′ prepared from 2,7-bis(4-trimellitimidophenoxy) naphthalene and aromatic diamines. © 1994 John Wiley & Sons, Inc.     

Diisocyanate route as a convenient method for the preparation of novel optically active poly(amide-imide)s based on N-trimellitylimido-S-valine

A new class of optically active poly(amide-imide)s based on an α-amino acid was synthesized via direct polycondensation reaction of different diisocyanates with a chiral diacid monomer. The step-growth polymerization reactions of N-trimellitylimido-S-valine (TISV) (1) with 4,4′-methylene-bis(4-phenylisocyanate) (MDI) (2) was performed under microwave irradiation, as well as solution polymerization under graduate heating and reflux conditions. The optimized polymerization conditions for each method were performed with tolylene-2,4-diisocyanate (TDI) (3), hexamethylene diisocyanate (HDI) (4), and isophorone diisocyanate (IPDI) (5) to produce optically active poly(amide-imide)s via diisocyanate route. The resulting polymers have inherent viscosities in the range of 0.02-1.10 dL/g. Decomposition temperatures for 5% weight loss (T₅) occurred above 300 °C (by TGA) in nitrogen atmospheres. These polymers are optically active, thermally stable and soluble in amide-type solvents. Some structural characterization and physical properties of this new optically active poly(amide-imide)s are reported.     

New poly(amide-imide)s syntheses. I. Soluble high-temperature poly(amide-imide)s derived from 2,5-bis(4-trimellitimidophenyl)-3,4-diphenylthiophene and various aromatic diamines

Novel aromatic poly(amide-imide)s with high inherent viscosities were prepared by direct polycondensation reaction of 2,5-bis(4-trimellitimidophenyl)-3,4-diphenylthiophene ( IV ) and aromatic diamines using triphenyl phosphite in the N-methyl–2-pyrrolidone (NMP)/pyridine solution containing dissolved CaCl₂. The diimide-diacid IV was readily obtained by the condensation reaction of 2,5-bis(4-aminophenyl)-3,4-diphenylthiophene ( III ₁) with trimellitic anhydride. The obtained poly(amide-imide)s showed high thermostability. Their decomposition temperatures at 10% weight loss in nitrogen atmospheres were above 550°C and the anaerobic char yield at 800°C ranged from 48 to 68%. Almost all the poly(amide-imide)s showed high glass transition temperatures above 300°C by differential scanning calorimetry (DSC) measurements. These polymers were readily soluble in various organic solvents and could be cast into transparent, tough, and flexible films. Their casting films showed obvious yield points in the stress-strain curves and had strength at break up to 74.2 MPa, elongation to break up to 70.1%, and initial modulus up to 4.56 GPa. The factors affecting the reaction of diimide-diacid IV and 4,4′-oxydianiline in view of monomer concentration, reaction temperature, and amount of CaCl₂ were also investigated. © 1992 John Wiley & Sons, Inc.     

Gas separation properties of aromatic poly(amide-imide) membranes

Aromatic poly(amide-imide)s were synthesized using direct 2,2-bis[N-(4-carboxyphenyl)-phthalimidyl] hexafluoropropane (6FDIA) polycondensation with various diamines containing flexible ether groups and bulky substituents. The oxygen and nitrogen gas transport in the poly(amide-imide) membranes was investigate at 35 °C with the pressure between the interval at 2-10 atm. The proposed method is expected to promote the gas permeability of the poly(amide-imide) membrane and maintain the gas selectivity. It was found that both gas permeability and selectivity of poly(amide-imide) membranes increased with increasing fractional free volume and d-spacing. The gas permeability had good correlation with the γ-transition temperature. The bulky pendent group introduced into diamine moiety of poly(amide-imide) could efficiently promote the gas permeability. For the behaviors of gas separation, the gas diffusivity coefficient and solubility selectivity controlled the gas permeability and selectivity, respectively. The sorption behavior of the aromatic poly(amide-imide) membranes can be well explained using the dual mode sorption model. The Langmuir capacity constant and Henry’s law constant increase with FFV increasing. 6F-TBAPS has the best O₂/N₂ separation performance among the poly(amide-imide) membranes.     

Synthesis and characterization of optically active and organosoluble poly(amide-imide)s containing imidazole rings as pendent groups by direct polycondensation

Six new optically active poly(amide-imide)s(PAIs) 6a-f were prepared by direct polycondensation reaction of N-trimelli-tylimido-L-histidine 4 as a chiral diacid with various aromatic diamines 5a-f.Triphenyl phosphite(TPP)/pyridine(Py) in the presence of calcium chloride(CaCl2) and N-methyl-2-pyrrolidone(NMP) were successfully applied to direct polycondensation reaction.The resulting new polymers were in good yields,and had inherent viscosities ranging between 0.29 and 0.41 dL g-1 and were detected with elem...     

New poly(amide-imide) syntheses. XII. Preparation and properties of poly(amide-imide)s based on the diimide-diacid condensed from 9,9-bis[4-(4-aminophenoxy)phenyl] fluorene and trimellitic anhydride

A dicarboxylic acid ( I ) was prepared from the condensation of 9,9-bis[4-(4-aminophenoxy) phenyl] fluorene and trimellitic anhydride. A new family of poly(amide-imide)s having inherent viscosities of 0.75-1.04 dL/g was prepared by the triphenyl phosphite activated polycondensation from the diimide-diacid I with various aromatic diamines in a medium consisting of N-methyl-2-pyrrolidone (NMP), pyridine, and calcium chloride. Most of the resulting polymers showed an amorphous nature and were readily soluble in polar solvents such as NMP and N,N-dimethylacetamide. All the soluble poly(amide-imide)s afforded transparent, flexible, and tough films. The glass transition temperatures of these polymers were in the range of 262–325°C and the 10% weight loss temperatures were above 525°C in air. © 1994 John Wiley & Sons, Inc.     

Preparation and Characterization of New Optically Active Poly(amide-imide)s from N,N′-(bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetra carboxylic)-bis-L-isoleucine and Aromatic Diamines

Five new optically active aromatic poly(amide-imide)s (PAIs) 5a–e were prepared from a direct polycondensation reaction of a new diacid of N,N′-(bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetra carboxylic)-bis-L-isoleucine 3 with various aromatic diamines 4a–e in a medium consisting of triphenyl phosphite (TPP), calcium chloride (CaCl₂), pyridine (Py) and N-methyl-2-pyrrolidone (NMP). The polycondensation reaction produced a series of novel poly(amid-imide)s 5a–e in quantitative yields with inherent viscosities of 0.39–0.51 dL/g. The resulting polymers were fully characterized by means of ¹H-NMR, FT-IR spectroscopy, elemental analyses, inherent viscosity, solubility test, specific rotation and thermal properties of them were investigated using TGA/DTG and differential scanning calorimeter (DSC). The diacid 4 was synthesized by the condensation reaction of bicyclo[2,2,2]oct-7-ene-2,3,5,6- tetracarboxylic dianhydride 1 with L-isoleucine 2 in acetic acid solution.     

Novel poly(amide-imide)s from 2,6-bis(5-amino-1-naphthoxy) pyridine

Reaction of 5-amino-1-naphthol with 2,6-dichloropyridine resulted in preparation of 2,6-bis(5-amino-1-naphthoxy) pyridine (AN). This pyridine-based ether diamine was reacted with two moles of trimellitic anhydride (TMA) to synthesize related diimide-diacid (DIDA). Direct polycondensation reaction of DIDA with different diamines in the presence of triphenyl phosphite (TPP) afforded seven different poly(amide-imide)s. All the polymers were characterized and their physical and thermal properties were studied. The inherent viscosity of the polymers was about 0.44-0.50 dl g⁻¹ and they showed high thermal stability.