Synthesis and characterization of soluble aromatic polyamides from 2,5-bis(4-aminophenyl)—3,4-diphenylthiophene and aromatic diacid chlorides

New soluble aromatic polyamides with inherent viscosities of 1.0–1.7 dL/g were prepared by the low temperature solution polycondensation of 2,5-bis(4-aminophenyl)—3,4-diphenylthiophene, bis(4-aminophenyl) ether, and aromatic diacid chlorides in N,N-dimethylacetamide. The polyamides and copolyamides are generally soluble in amide-type solvents. They have glass transition temperatures in the range of 280–325°C and showed no weight loss below 390°C on thermogravimetry curves in both air and nitrogen atmospheres.     

Synthesis and characterization of aromatic polyamides from 1,1-bis(4-aminophenyl)-2,2-diphenylethylene and aromatic diacid chlorides

Novel, soluble aromatic polyamides and copolyamides containing tetraphenylethylene units were prepared by the low temperature solution polycondensation of 1,1-bis(4-aminophenyl)-2,2-diphenylethylene and aromatic diamines with various aromatic diacid chlorides. Highmolecular-weight polyamides having inherent viscosities of 0.6–1.5 dL/g and number-average molecular weight above 21000 were obtained quantitatively. These polymers were readily soluble in various solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide (DMAc), and dimethyl sulfoxide and gave pale yellow, transparent, flexible films by casting from DMAc solution. The polymers had glass transition temperatures between 290 and 340°C, and started to lose weight around 400°C, with 10% weight loss being recorded at about 470°C in air.     

Synthesis and characterization of new soluble aromatic polyamides from diaminotetraphenylimidazolin-2-one and various aromatic dicarboxylic acid chlorides

Novel aromatic polyamides, having inherent viscosities of 0.76-2.31 dL/g, were synthesized by the low temperature solution polycondensation of a new highly phenylated diamine monomer having an imidazolinone group, 1,3-bis(4-aminophenyl)-4,5-diphenylimidazoline-2-one (TPIDA), with various aromatic diacid chlorides. All the polymers were amorphous, and most of the polyamides were readily soluble in organic solvents such as N-methyl–2-pyrrolidone, N,N-dimethylacetamide (DMAc), and m-cresol. Flexible and tough films could be prepared from the DMAc solutions of these soluble aromatic polyamides. The glass transition temperatures and 10% weight loss temperatures under nitrogen of the polyamides were in the range of 275–315°C and 430–505°C, respectively. © 1995 John Wiley & Sons, Inc.     

Synthesis and characterization of novel aromatic polyamides from 3,4-bis(4-aminophenyl)-2,5-diphenylpyrrole and aromatic diacid chlorides

A new polymer-forming monomer, 3,4-bis(4-aminophenyl)-2,5-diphenylpyrrole, was synthesized in three steps starting from 4′-nitrodeoxybenzoin. Tetraphenylpyrrole-containing aromatic polyamides and copolyamides were prepared from the diamine with various aromatic diacid chlorides and from a mixture of the diamine and 4,4′-oxydianiline with terephthaloyl chloride, respectively. The resultant polymers had inherent viscosities in the 0.3–1.8 dL/g range and were generally soluble in various organic solvents including N,N-dimethylacetamide and m-cresol. They have glass transition temperatures in the range of 306–333°C and showed no weight loss below 380°C in both air and nitrogen atmospheres.     

Synthesis and characterization of novel aromatic polyamides from 3,4-bis(4-aminophenyl)-2,5-diphenylfuran and aromatic diacid chlorides

A new highly phenylated heterocyclic diamine, 3,4-bis(4-aminophenyl)-2,5-diphenylfuran, was synthesized in three steps from 4–-nitrodeoxybenzoin. The low temperature solution polycondensation of the diamine with various aromatic diacid chlorides afforded tetraphenylfuran-containing aromatic polyamides with inherent viscosities of 0.2–0.8 dL/g. Copolyterephthalamides were obtained from the diamine and 4,4′-oxydianiline. The polyamides were generally soluble in a wide range of solvents that included N,N-dimethylacetamide, N-methyl-2-pyrrolidone, pyridine, and m-cresol. Glass transition temperatures of the polyamides and copolyamides ranged from 302–342°C, and 10% weight loss was observed above 480°C in nitrogen.     

Preparation and properties of disilane-containing photodegradable aromatic polyamides from bis(p-aminophenyl)tetramethyldisilane and aromatic diacid chlorides

1,2-Bis(p-aminophenyl)tetramethyldisilane was synthesized from 1,2-dichlorotetramethyldisilane and 4-[N,N-bis(trimethylsilyl)amino]phenyllithium. The diamine was reacted with various aromatic diacid chlorides giving disilane-containing aromatic polyamides (aramids), whose inherent viscosities were between 0.27 and 0.70 dL/g, depending on the diacid chlorides used. The aramids had glass transition temperatures between 194 and 255°C. No weight loss was observed below 350°C. Some of the polymers were found to be semicrystalline based on their x-ray diffractograms. The aramid films showed a strong ultraviolet (UV) absorption at 287 nm, which decreased during irradiation with UV light, suggesting that cleavage of the silicon-silicon bond in the aramid backbone occurs. A decrease in the inherent viscosity and molecular weight of the soluble aramid derived from phenylindanedicarbonyl chloride was also observed by irradiation with UV light.     

Synthesis and characterization of new soluble aromatic polyimides from 3,4-bis (4-aminophenyl)-2,5-diphenylfuran and aromatic tetracarboxylic dianhydrides

New soluble polyimides with inherent viscosities of 0.2–0.6 dL/g were synthesized from 3,4-bis (4-aminophenyl)-2,5-diphenylfuran and various aromatic tetracarboxylic dianhydrides by the conventional two-step method which involved ring-opening polyaddition and subsequent cyclodehydration. Almost all of the polymides were generally soluble in a wide range of organic solvents such as N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolidone, m-cresol, o-chlorophenol, and pyridine. The polyimide prepared from pyromellitic dianhydride was crystalline, whereas the other polyimides were amorphous. All the polyimides have glass transition temperatures in the range of 281–344°C and showed no appreciable weight loss up to 410°C in both air and nitrogen atmospheres.     

Synthesis and characterization of new soluble aromatic polyimides from 3,4-bis(4-aminophenyl)-2,5-diphenylpyrrole and aromatic tetracarboxylic dianhydrides

Novel aromatic polyimides containing tetraphenylpyrrole unit were synthesized from 3,4-bis(4-aminophenyl)-2,5-diphenylpyrrole and various aromatic tetracarboxylic dianhydrides by the usual two-step procedure that included ring-opening polyaddition and subsequent thermal cyclodehydration. These polymers had inherent viscosities in the 0.20–0.65 dL/g range and were practically amorphous as shown by the X-ray diffraction studies. All the polyimides except for polypyromellitimide were easily soluble in a wide range of organic solvents such as o-chlorophenol, pyridine, 1,3-dimethyl-2-imidazolidone, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone at room temperature. These polyimides had high glass transition temperatures of 302–359°C and exhibited 10% weight loss at temperatures above 510°C in nitrogen.     

Preparation and properties of new aromatic polyamides from bis(4-aminophenyl) phenylphosphine and aromatic dicarboxylic acids

A new triphenylphosphine-type monomer, bis(4-aminophenyl) phenylphosphine, was synthesized starting from p-bromoaniline and dichlorophenylphosphine. The aromatic polyamides (aramids) containing triphenyphosphine unit in the polymer backbone was prepared by the polycondensation of this diamine with various aromatic diacid chlorides using a low-temperature solution method in N,N-dimethylacetamide (DMAc). The aramids having inherent viscosities of 0.4–0.7 dL/g were obtained in quantitative yields. The polymers were amorphous and soluble in various organic solvents such as DMAc, N-methylpyrrolidone, dimethyl sulfoxide, pyridine, and m-cresol. Transparent, tough, and flexible films were obtained by casting from the DMAc solutions. The glass transition temperatures of the aramids were in the range of 265–310°C, and the 10% weight loss temperatures were above 400°C in air. © 1993 John Wiley & Sons, Inc.     

Synthesis and characterization of new soluble aromatic polyimides from diaminotetraphenylimidazolinone and aromatic tetracarboxylic dianhydrides

A series of new soluble aromatic polyimides with inherent viscosities of 0.65–1.12 dL/g were synthesized from 1,3-bis(4-aminophenyl)-4,5-diphenylimidazolin-2-one and various aromatic tetracarboxylic dianhydrides by the conventional two-step procedure that included ring-opening polyaddition and subsequent thermal cyclodehydration. These polyimides could also be prepared by the one-pot procedure in homogeneous m-cresol solution. Most of the tetraphenyl-pendant polyimides were soluble in organic solvents such as N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolidone, and m-cresol. Some polyimides gave transparent, flexible, and tough films with good tensile properties. The glass transition temperatures and 10% weight loss temperatures under nitrogen of the polyimides were in the range of 287–326 and 520–580°C, respectively. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1767–1772, 1998     

Synthesis and characterization of aromatic polythiazole-amides from new aromatic diamines containing phenyl-pendant thiazole units

New aromatic diamines containing phenyl-pendant thiazole units were synthesized in three steps starting from p-nitrobenzyl phenyl ketone. Novel aromatic polyamides containing phenyl-pendant thiazole units were prepared by the low-temperature solution polyconden-sation of 1,4- (or 1.3-) bis[5-(p-aminophenyl)-4-phenyl-2-thiazolyl] benzene with various aromatic dicarboxylic acid chlorides in N,N-dimethylacetamide. High molecular weight polyamides having inherent viscosities of 0.5–3.0 dL/g were obtained quantitatively. The polythiazole-amides with m-phenylene, 4,4′-oxydiphenylene, and 4,4′-sulfonyldiphenylene units were soluble in N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and pyridine, and gave transparent flexible films by casting from the solutions. These organic solvent-soluble polyamides displayed prominent glass transition temperatures (T_g) between 257 and 325°C. On the other hand, the polythiazole-amides with p-phenylene and 4,4′-biphenylene units were insoluble in most organic solvents, and had no observed T_g. All the polythiazole-amides started to decompose at about 400°C with 10% weight loss being recorded at 450–525°C in air. © 1995 John Wiley & Sons, Inc.     

Synthesis and characterization of N-phenylated aromatic polyureas from N,N′ -dichloroformyl-p-dianilinobenzene and N,N′ -bistrimethylsilyl-diamines

NovelN-phenylated aromatic polyureas having inherent viscosities of 0.13–0.35 dL/g were synthesized by the solution polycondensation of N,N′-dichloroformyl-p-dianilinobenzene with N,N′-bistrimethylsilyl derivatives of bis(4-aminophenyl)ether, piperazine, and p-dianilinobenzene in sulfolane. Except the polyurea containing piperazine unit, the other polyureas were amorphous and readily soluble in a variety of organic solvents such as tetrahydrofuran. The polyurea derived from p-dianilinobenzene, which has no vulnerable hydrogen on the urea linkage, did not melt below 350°C and was stable up to 450°C in air.     

Synthesis and characterization of soluble aromatic polyurea-amides from new N,N′--dimethyl-N,N′-bis(aminophenyl)ureas and aromatic dicarboxylic acid chlorides

Aromatic polyurea-amides having inherent viscosities of 0.36–0.67 dL/g were synthesized by the low temperature solution polycondensation of new N,N′-dimethyl-N,N′-bis(aminophenyl)ureas with various aromatic dicarboxylic acid chlorides. All the polymers were amorphous, and most of them were soluble in a variety of organic solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide (DMAc), m-cresol, and pyridine. Some of the polymers could be cast from the DMAc solutions into transparent and flexible films having good tensile properties. The glass transition temperatures of the polyurea-amides obtained from the bis(4-aminophenyl)-substituted ureas were 244–272°C. The temperatures of 10% weight loss under nitrogen of the polymers were in the range of 430 and 480°C. © 1995 John Wiley & Sons, Inc.     

Preparation and Properties of Novel Aromatic Polyamides from Diamines Containing 4,5-Imidazolediyl Structure

Novel aromatic polyamides were prepared from aromatic diamine containing 4,5-imidazolediyl unit, either by low temperature solution polycondensation or by direct polycondensation. Used diamines were 4,5-bis(4-aminophenyl)-2-phenylimidazole 1, 4,5-bis[4-(4-aminophenyl)]-2-(4-methylphenyl)imidazole 2 and 4,5-bis[4-(4-aminophenoxy)phenyl]-2-phenylimidazole 3. The obtained aromatic polyamides were produced with moderate to high inherent viscosity and soluble in polar aprotic solvents such as N,N-dimethylacetamide (DMAc), 1-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). Thermogravimetric analysis showed those polymers were stable up to 422°C in nitrogen atmosphere. The glass transition temperature (T _g)s of the polymers derived from diamine 3 were in the range between 243 and 275°C, and these values were approximately 120–160°C lower than those analogue polyamide I series containing no phenoxy units. The properties of polyamide I series are also compared with those of analogue polymers that order of aromatic nuclei and amide linkage is reversible.     

Preparation and properties of fluorine-containing aromatic polyamides from tetrafluorophthaloyl chlorides and aromatic diamines

New fluorine-containing aromatic polyamides with inherent viscosities of 0.4–1.8 dL/g were prepared by the low temperature solution polycondensation of tetrafluoroisophthaloyl and tetrafluoroterephthaloyl chlorides with N,N′-bis(trimethylsilyl)-substituted aromatic diamines. The aromatic polyperfluoroisophthalamides were amorphous polymers with glass transition temperatures around 280°C, whereas the polyperfluoroterephthalamides were crystalline. Most of these aromatic polyamides were soluble in organic solvents, and began to decompose around 330°C in air or nitrogen atmosphere.     

Polypyrazoles from aromatic dipropynones and aromatic dihydrazines

Two types of polypyrazoles, unsubstituted and phenylated, were prepared by a novel synthetic route involving the cyclopolycondensation of aromatic dihydrazines and aromatic dipropynones. The polymers had inherent viscosities as high as 1.05 dL/g and were soluble in N, N-dimethylacetamide, chloroform (phenylated polypyrazoles only), and sulfuric acid. The polymers exhibited glass transition temperatures ranging from 202 to 266°C and polymer decomposition temperatures (10% weight loss) as measured by thermogravimetric analysis of 400–500°C in air and 465–512°C in nitrogen. The synthesis and characterization of several polypyrazoles are discussed.     

Preparation and properties of new photosensitive polyimides from bis(4-aminophenyl)tetramethyldisilane and various aromatic tetracarboxylic dianhydrides

New photosensitive polymides containing photosensitive disilane unit were synthesised from 1,2-bis(4-aminophenyl)tetramethyldisilane and various aromatic tetracarboxylic dianhydrides by the usual two-step procedure that includes ring-opening polyaddition to yield the precursor polyamic acids, followed by cyclodehydration giving the respective polyimides. The polymaic acids had inherent viscosities between 0.63 and 0.85 dL/g depending on the tetracarboxylic dianhydride used. Excepting the polyimide obtained from pyromellitic dianhydride, all other polyimides were soluble in N-methyl-2-pyrrolidone, m-cresol, and pyridine. While the polyimide containing diphenyl sulfone unit was amorphous, the other polyimides were semi-crystalline polymers based on their x-ray diffractograms. The polyimides had glass transition temperatures between 235 and 304°C. They were thermally stable up to 380°C in both air and nitrogen atmospheres. All the polyamic acids showed a drastic decrease in the inherent viscosity upon UV light irradiation, implying the inherent photosensitivity of the polymers containing the disilane moiety.     

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 and characterization of new aromatic polyesters and polyethers derived from 1,2-bis(4-hydroxyphenyl)-1,2-diphenylethylene

New polyarylates and aromatic polyethers were synthesized from 1,2-bis(4-hydroxyphenyl)-1,2-diphenylethylene, and aromatic dicarboxylic acid chlorides and aromatic dihalides, respectively. The polyarylates having inherent viscosities of 0.28–1.05 dL/g were synthesized by either the two-phase method or the high-temperature solution method. All the polymers were easily soluble in N-methyl-2-pyrrolidone, N,N-dimethylformamide, pyridine, m-cresol, 1,4-dioxane, and 1,1,2,2-tetrachloroethane. They have glass transition temperatures in the range of 217–250°C and showed no weight loss below 315°C in both air and nitrogen atmospheres. Aromatic polyethers with inherent viscosities of 0.85–1.21 dL/g were obtained by the polycondensation of 1,2-bis(4-hydroxyphenyl)-1,2-diphenylethylene and aromatic difluorides in the presence of potassium carbonate. These polymers having glass transion temperatures of 193–220°C were also soluble in the aforementioned solvents and stable up to around 350deg;C in both atmospheres. © 1994 John Wiley & Sons, Inc.     

Synthesis and characterization of phenyl-pendant aromatic polythiazoles from bis-α-bromophenylacetyl compounds and dithioamides

Novel phenyl-pendant aromatic polythiazoles having inherent viscosities of 0.3–1.3 dL/g were synthesized by the solution polycondensation of bis[4-(α-bromophenylacetyl)phenyl] ether with aromatic dithioamides or dithiooxamide in dimethylformamide at 60°C. The polythiazole having m-phenylene linkage was readily soluble in chloroform and m-cresol, and transparent flexible film could be cast from the chloroform solution. Glass transition temperatures of these polythiazoles were in the range of 210–250°C. They started to decompose at about 500°C in air with 10% weight loss being recorded at around 570°C.