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 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 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 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.     

Unsaturated alkoxy‐substituted poly(p‐phenylene 1,3,4‐oxadiazole)s: Synthesis and chemical–physical characterization

A new series of alkoxy‐substituted poly(p‐phenylene 1,3,4‐oxadiazole)s modified by the insertion of small percentages of various comonomers were synthesized through the precursor polyhydrazides. The comonomers used contained trans double bonds or meta‐alkoxy‐substituted aromatic rings to improve the solubility of the final polymers. The synthesized copolymers were chemically characterized by ¹H NMR and Fourier transform infrared spectroscopy. In some cases, the copolymers really showed improved solubility in organic solvents. The ¹⁵N solid‐state NMR technique was applied to examine the degree of conversion from the precursor polyhydrazides to the final polymers, which determined the effective conjugated length in the target polyoxadiazoles. Thermal stability and structural characteristics of all the polymers as well as a preliminary investigation on the optical properties of polyoxadiazoles are also reported. The copolymers retained high absorbance in the UV region and high transmission in the whole telecommunication range. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3916–3928, 2003     

Synthesis and characterization of new soluble aromatic polyamides derived from 1,4‐Bis(4‐carboxyphenoxy)‐2, 5‐di‐tert‐butylbenzene

Aromatic polyamides based on a novel bis(ether‐carboxylic acid) were synthesized by the direct phosphorylation condensation method. 1,4‐Bis(4‐carboxyphenoxy)‐2,5‐di‐tert‐butylbenzene was combined with various diamines containing flexible linkages and side substituents to render a set of eight novel aromatic polyamides. The polymers were produced with high yields and moderate to high inherent viscosities (0.49–1.32 dL/g) that corresponded to weight‐average and number‐average molecular weights (by gel permeation chromatography) of 31,000–80,000 and 19,000–50,000, respectively. Except for a single example, the polyamides were essentially amorphous and soluble in a variety of common solvents such as cyclohexanone, dioxane, and tetrahydrofuran. They showed glass‐transition temperatures of 250–295 °C (by differential scanning calorimetry) and 10% weight loss temperatures above 460 °C, as revealed by thermogravimetric analysis in nitrogen. Polymer films, obtained by casting from N,N‐dimethylacetamide solutions, exhibited good mechanical properties, with tensile strengths of 83–111 MPa and tensile moduli of 2.0–2.2 GPa. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 475–485, 2001     

Synthesis and characterization of new fluorescent poly(arylene ether)s

The poly(arylene ether)s were prepared by the nucleophillic aromatic substitution polymerization of phenolphthalin and its derivatives with activated aromatic difluorides. The polymers had glass transition temperatures ranging from 210 to 240°C. Though the monomers have no fluorescence, the resulting polymers fluoresced a light green color in solid and solution states. The maximum excitation and emission wavelengths are 420 nm and 470 nm, respectively. In the polymer solutions, the fluorescence intensity decreased gradually, but the intensity was recovered by heating the polymer at 220°C for a few minutes. The fluorescent polymer had a stable radical. A model compound having the same repeating unit of the polymer was also prepared. The fluorescence properties of this model were almost the same as those of the polymers. © 1994 John Wiley & Sons, Inc.     

Synthesis and characterization of soluble aromatic polyesters derived from substituted terphenyl and quinquephenyl diols

Rigid aromatic polyesters containing alkoxy or phenyl-substituted oligophenyls were prepared. Soluble polymers were obtained also in cases where phenyl-substituted quinquephenyl diols were combined with asymmetric phenyl-substituted terephthalic acid. The synthesized polyesters were characterized by viscosimetry, gel permeation chromatography, thermal analysis, and dynamic mechanical analysis. The temperature dependence of the intrinsic viscosity was sensitive to the type of side groups. Thermogravimetry has shown that polyesters with aromatic substituents were stable up to 380–400°C. The glass transition temperatures of the polyesters with aromatic side groups were in the 220–260°C range as determined by DSC. Polyesters with hexyloxy side chains show crystallinity. Dynamic mechanical analysis showed that in the cases where aromatic substituents were used to increase solubility, the obtained polymers have very useful mechanical properties at high temperatures. The polymer having the quinquephenyl unit in the main chain has an almost constant modulus up to 340°C. © 1996 John Wiley & Sons, Inc.     

Synthesis and characterization of new polybenzimidazopyrrolones derived from pyridine‐bridged aromatic tetraamines and dianhydrides

A series of new polybenzimidazopyrrolones (polypyrrolone, PPy) were synthesized by polycondensation of pyridine‐bridged aromatic tetraamines, including 2,6‐bis (3′,4′‐diaminophenyl)‐4‐phenylpyridine and 2,6‐bis(3′,4′‐ diaminophenyl)‐4‐(3″‐trifluoromethyl)phenyl pyridine, with various aromatic dianhydrides. Experimental results indicated that the PPys, multiaromatic conjugated and semiladder polymers, showed good thermal stabilities with thermal‐decomposition temperatures of about 500 °C and residual weight retention at 750 °C as high as 84%. PPy films could be obtained by casting the precursor solution, poly(amide amino acid) on glass substrate, followed by thermal dehydrating at elevated temperatures. The polymer films exhibited excellent alkaline hydrolysis resistance, which retained their original shapes and toughness after boiling 7 days in 10% sodium hydroxide solution. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1845–1856, 2004     

Synthesis and characterization of organosoluble ditrifluoromethylated aromatic polyimides

Two novel diamine monomers, 1,4‐bis (4‐aminophenoxy)‐2‐[(3′,5′‐ditrifluoromethyl)phenyl]benzene and 1,4‐bis [2′‐cyano‐3′(4″‐amino phenoxy)phenoxy]‐2‐[(3′,5′‐ditrifluoromethyl)phenyl] benzene, were synthesized from (3,5‐ditrifluoromethyl)phenylhydroquinone. A series of ditrifluoromethylated aromatic polyimides derived from the diamines were prepared through a typical two‐step polymerization method. These polyimides had a high thermal stability, and the temperatures at 10% weight loss were above 507 °C in nitrogen. Most of the polymers showed good solubility in anhydrated 1‐methyl‐2‐pyrrolidone, N,N‐dimethylacetamide, N,N‐dimethylformamide, chloroform, and tetrahydrofuran at room temperature. All the polymers formed transparent, strong, and flexible films with tensile strengths of 63.6–95.8 MPa, elongations at break of 5–10%, and Young's moduli of 2.38–2.96 GPa. The dielectric constants estimated from the average refractive indices are 2.69–2.89. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3018–3029, 2005     

Thermal characterization of modified phyllosilicates with aromatic heterocyclic amines

Vermiculite with the general formula of [Si_6.85Al_1.15][Mg_4.68Al_0.51Fe_0.63]O₂₀(OH)₄Ca_0.128Na_0.032K_0.094 was made to react with heteroaromatic amines α-, β- and γ-picolines in aqueous solution. The products were characterized by elemental analysis, infrared spectroscopy, X-ray diffraction and thermogravimetry. The intercalated nanocompounds maintained the crystallinity which changed the original interlayer distance of 1422 to 1474, 1456 and 1474 pm, for the sequence of the guest picoline molecules. Thermogravimetry data suggested the intercalation reactions were governed by basicity of amines.     

Synthesis and gas transport properties of new aromatic 3F polymers

New aromatic 3F polymers were obtained from condensations of 2,2,2-trifluoroacetophenone (1) with biphenyl (a), terphenyl (b), a mixture of biphenyl with terphenyl (ab), phenyl ether (c) and diphenoxybenzophenone (d). The reactions were performed at room temperature in the Brønsted superacid trifluoromethanesulfonic acid (TFSA) and in a mixture of TFSA with dichloromethane. The polymers show high glass transition temperatures >170 °C, excellent thermal stability (decomposition temperatures ≥475 °C) and good solubility in chlorinated solvents and strong acids. The 3F polymer structures based on biphenyl and terphenyl show attractive permeability coefficients for CO₂ (∼200 Barrers) and H₂ (∼120 Barrers), whereas the 3F polymers that contain ether linkages have permeability coefficients in the typical range of regular polysulfone and polycarbonate. However, in sharp contrast to polysulfone and polycarbonate families, new 3F polymers possess high chemical stability and they have advantages since their reactions, based on commercially available monomers, can be carried out in one-pot at room temperature and offer a large variety of structures not possible to prepare by other synthetic methods.     

Synthesis and characterization of aromatic polymers derived from 5‐perfluoroalkylisophthalic acid

A series of polyisophthalamides and polyisophthalates having perfluorinated side chains were prepared from 5‐perfluoroalkylisophthaloyl dichlorides. The aromatic polyamides and polyarylates synthesized by conventional low temperature solution polycondensation and interfacial polycondensation, respectively, had inherent viscosities of 0.19 to 1.28 dL g⁻¹ in yields of 65 to 100%. Solubilies of the resulting polymers were improved by incorporating nonafluorobutyl groups but not improved by incorporating heptadecafluorooctyl groups. Although the effect on the glass transition temperature (T_g) of incorporating perfluoroalkyl groups into the aromatic polyamides or polyarylate backbone is great, the incorporation maintained the thermal stability of the polymers. In spite of the rigid nature of perfluoroalkyl groups, T_gs were decreased by incorporating perfluoroalkyl groups. The value of the contact angle of water on the aromatic polyamides films gradually increased with incorporation of the perfluoroalkyl groups. On the other hand, the value of the contact angle remarkably increased when perfluoroalkyl groups were incorporated into polyarylates. The Owens γs were also calculated for some aromatic polyamides by measuring contact angles of diiodomethane on the polymer films. The γs were estimated at 23‐37 mN m⁻¹ and about 10% of them were contributed by hydrogen bonding. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1135–1141, 1999     

Synthesis and properties of aromatic polyureas from N,N′-bis(trimethylsilyl)-substituted aromatic diamines and aromatic diisocyanates

Silylated aromatic polyureas were synthesized by the polyaddition of N,N′-bis(trimethylsilyl)-substituted aromatic diamines to aromatic diisocyanates in various organic solvents at a temperature ranging from 30 to 100°C. Colorless and transparent films of the silylated polyureas were obtained by casting directly from these solutions in a dry nitrogen atmosphere. The silylated polyureas thermally decomposed at around 200°C and were easily desilylated with alcohol to convert to almost amorphous aromatic polyureas having inherent viscosities of 0.4–1.0 dL/g. The polyureas exhibited better solubility in organic solvents such as N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide and had somewhat lower thermal decomposition temperatures (around 300°C) than the polyureas prepared by a conventional method from the parent aromatic diamines and diisocyanates.     

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.     

Poly(DCAQI): Synthesis and characterization of a new redox‐active polymer

Redox‐active anthraquinone based polymers are synthesized by the introduction of a polymerizable vinyl and ethynyl group, respectively, resulting in redox‐active monomers, which electrochemical behaviors are tailored by the modification of the keto groups to N‐cyanoimine moieties. These monomers can be polymerized by free radical polymerization and Rh‐catalyzed polymerization methods, respectively. The resulting polymers are obtained in molar masses (M_n) of 4,400 to 16,800 g mol^?1 as well as high yields of up to 97%. The monomers and polymers are furthermore electrochemically characterized by cyclic voltammetry. The monomers exhibit two one‐electron redox reactions at about ?0.6 and ?1.0 V versus Fc⁺/Fc. The N‐cyanoimine units are, however, partially hydrolyzed during the polymerization step or during the electrochemical measurements and degenerate to carbonyl groups, resulting in a new reduction signal at ?1.26 V versus Fc⁺/Fc. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1998–2003     

Synthesis and characterization of aromatic polymers containing pendant silyl groups. II. Aromatic polyamides

In order to improve the solubility of aromatic polyamides without significant loss of thermal stability, synthesis of aromatic polyamides containing pendant silyl groups was carried out by direct polycondensation of silylated aromatic diacids such as 2-trimethylsilylterephthalic acid (TSTA), 2,5-bis (trimethylsilyl) terephthalic acid (BTSTA), 5-trimethylsilylisophthalic acid (TSIA), 5-dimethylphenylsilylisophthalic acid (DMSIA), and 5-triphenylsilylisophthalic acid (TPSIA) with various aromatic diamines. The resulting polyamides had inherent viscosities in the range of 0.18–1.10 dL/g and showed improved solubilities toward aprotic polar solvents such as NMP, DMF, DMSO, etc. The prepared aromatic polyamides exhibited fairly good thermal stabilities, which were almost comparable to those of corresponding nonsubstituted aromatic polyamides. That is, thermogravimetric analysis (TGA) data revealed 10% weight losses at 358–500°C and residual weights at 700°C were 46–67% under nitrogen atmosphere. © 1992 John Wiley & Sons, Inc.     

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 properties of new soluble aromatic polybenzoxazoles from 4,4′-diamino-3,3′-dihydroxytriphenylamines and aromatic dicarboxylic acids

Two new triphenylamine-based bis (o-aminophenol) monomers, 4,4′-diamino-3,3′-dihydroxytriphenylamines, were successfully synthesized by the cesium fluoride-mediated condensation of 2-(benzyloxy)-4-fluoronitrobenzene with aniline derivatives, followed by simultaneous deprotection and reduction. Aromatic polybenzoxazoles having inherent viscosities of 0.58–1.05 dL/g were obtained by the low-temperature solution polycondensation of the bis(aminophenol)s with various aromatic dicarboxylic acid chlorides and the subsequent thermal cyclodehydration of the resultant poly(hydroxyamide)s. All the polybenzoxazoles were amorphous, and most of them were soluble in organic solvents such as m-cresol and o-chlorophenol. Flexible and tough films of polybenzoxazoles could be cast from the DMAc solutions of some aromatic poly(hydroxyamide)s, followed by thermal cyclodehydration. The glass transition temperatures and 10% weight loss temperatures of the polybenzoxazoles under nitrogen were in the range of 262–327 and 610–640°C, respectively. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1987–1994, 1998