Synthesis of polyamides from pseudo dibenzoylphthaloyl chlorides and aliphatic diamines

New pseudo dibenzoylphthaloyl chlorides, namely, 2,5-dibenzoylterephthaloyl, 4,6-dibenzoylisophthaloyl, and 4,6-di(p-toluyl)isophthaloyl chlorides, were synthesized as monomers. The ring-opening polyaddition reaction of the pseudo dibenzoylphthaloyl chlorides with aliphatic diamines in N-methyl-2-pyrrolidone afforded a new class of polyamides having inherent viscosities of 0.2 ～ 0.6 in quantitative yield. The solution polymerization was almost completed within 30 min at room temperature. All of the polyamides were soluble in a wide range of solvents including tetrahydrofuran. These polymers began to decompose at around 300°C both in air and under nitrogen as determined by differential thermal analysis (DTA) and thermogravimetric analysis (TGA).     

Synthesis of polybenzodipyrrolediones by thermal cyclodehydration of polyamides derived from dibenzylidenebenzodifurandiones and aliphatic diamines

A new class of polyheterocycles, polybenzodipyrrolediones (PBP), has been synthesized successfully by the two-step polymerization of dibenzylidenebenzodifurandiones with aliphatic diamines. New bislactone monomers, 3,5-dibenzylidene-3,5-dihydro-1H,7H-benzo[1,2-c:4,5-c′]difuran-1,7-dione and 3,7-dibenzylidene-3,7-dihydro-1H,5H-benzo[1,2-c:4,5-c′]-difuran-1,5-dione, were synthesized from pyromellitic dianhydride and phenylacetic acid. The ring-opening polyaddition reaction of the bislactones with aliphatic diamines in a polar solvent afforded novel polyamides having inherent viscosities of 0.1–1.0 in quantitative yield. The solution polymerization was almost completed within several hours at 80°C, while it required approximately a week to its completion at room temperature. Dimethyl sulfoxide and N-methyl-2-pyrrolidone were preferred solvents for the polymerization. The open-chain polyamides were subsequently cyclodehydrated by heating at 240°C to give PBP having high molecular weight. The aliphatic PBP were soluble in hot polar solvents such as N-methyl-2-pyrrolidone, m-cresol, and nitrobenzene. They began to decompose at about 400°C in a nitrogen atmosphere as determined by thermogravimetric analysis.     

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.     

Direct synthesis and properties of polybenzodipyrrolediones from dibenzylidenebenzodifurandiones and various diamines

Aromatic and aliphatic polybenzodipyrrolediones have been synthesized directly by the solution cyclopolycondensation of two dibenzylidenebenzodifurandiones with four different diamines in refluxing m-cresol or o-phenylphenol in the presence of boric acid. The polymerizations proceeded smoothly in a homogeneous solution and afforded the heterocyclic polymers having inherent viscosities as high as 1.0 almost quantitatively. All the polymers were readily soluble in a wide range of solvents, including N-methyl-2-pyrrolidone (NMP), hot m-cresol, and hot pyridine. Tough, transparent, yellow films could be cast from NMP solutions of the polymers. Thermogravimetric analysis of the aromatic polybenzodipyrrolediones showed a 10% weight loss temperature of 460–500°C under nitrogen. The results also indicated that the aromatic polymers were somewhat less thermally stable than wholly aromatic polypyromellitimides.     

Synthesis and characterization of silicon-containing polyamides from aromatic sulfone ether diamines and aromatic organosilicon diacid chlorides

New polymides and copolyamides containing silicon and sulfone ether linkages, soluble in common aprotic solvents and having inherent viscosities of 0.3–0.6 dL/g have been synthesized by solution condensation of bis-(4-chlorocarbonyl phenyl) dimethylsilance (DMSC) and/or bis-(4-chlorocarbonyl phenyl) diphenylsilance (DPSC) with 4,4′-[sulfonylbis-(4,1-phenylenoxy)] bisbenzenamine, 3,3′-[sulfonylbis (4,1-phenyleneoxy)] bisbenzenamine, and bis (4-aminophenyl) ether. These polymers were characterized by infrared spectra, solution viscosity, thermooxidative degradation, differential scanning calorimetry, and x-ray diffraction. These polymers show good thermal stability.     

Syntheses of stereoregular and optically active polyamides from active 4-chloro-1-benzotriazolyl diesters and diamines

A new route to prepare optically active polyamides was established, based on the polycondensation of two new active diesters: the active diesters of 4-chloro-1 hydroxybenzotriazole, such as 1,1'-(terephthaloyldioxy)bis(4-chloro-benzotriazole), and 1,1'-(isophthaloyldioxy)bis(4-chlorobenzotriazole), with optically active isomers of 2,4-diaminopentane. Dipolar aprotic solvents such as N,N-dimethylformamide and dimethyl sulfoxide were used as reaction solvents. The solution polycondensation carried out in solution at room temperature afforded optically active polyamides. The aminolysis of the two active diesters was carried out as a model reaction study.     

Synthesis of polyamides from linear bisanhydrides and diamines

The aminolysis of benzoic mesitoic anhydride was studied in a model system to select the reaction site by steric effect and was found to occur exclusively at the carbonyl group of the benzoic acid. Solution polycondensation of new linear bisanhydrides, terephthalic bis(mesitoic anhydride) and adipic bis(mesitoic anhydride), with aromatic diamines in polar aprotic solvents that contained lithium chloride at room temperature, afforded polyamides with high molecular weight. The interfacial polycondensation in a dichloromethane-water system also successfully yielded polyamides from aliphatic diamines.     

Stereoregular polyamides derived from methylene-L-tartaric acid and aliphatic diamines

Stereoregular polyamides containing two chiral backbone carbons in the repeating unit were prepared by polycondensation of bis(pentachlorophenyl) 2,3-O-methylene-L -tartrate with 1,9 and 1,12-alcanediamines activated as N,N′-bis(trimethylsilyl) derivatives. The polymers were characterized by elemental analysis, IR, and ¹H-NMR spectroscopy, and differential scanning calorimetry. Both viscosimetry and GPC were used to estimate the molecular weights which ranged between 6000 and 44000. These polytartaramides were readily soluble in chloroform, displayed moderate optical activity in solution, and formed highly crystalline films.     

Syntheses of polyamides and polypyrrolones from 2,2′-disubstituted bis(3-buten-4-olides) and diamines

The ring-opening polyaddition of 2,2′-disubstituted bis(3-buten-4-olides) with aliphatic diamines in m-cresol at room temperature afforded in quantitative yields polyamides with a pendant ketone moiety having inherent viscosities of up to 0.7. On the other hand, the polymerization in m-cresol at 80°C with acidic catalysts and at 160°C without any catalyst yielded directly polypyrrolones, a novel class of polyheterocycles. The cyclodehydration of the open-chain polyamides to polypyrrolones was also achieved by simply treating the polyamide films with methanolic hydrochloric acid at room temperature. Both of the polymers were generally soluble in hot polar solvents such as dimethylformamide, m-cresol, and nitrobenzene. The polypyrrolones began to lose weight gradually at around 250°C in nitrogen as determined by thermogravimetric analysis, while the thermograms in air showed an appreciable weight increase at about 230°C.     

Aromatic polyamides derived from unsymmetrical diamines containing the phthalazinone moiety

Two unsymmetrical and kink non‐coplanar heterocyclic diamines, 1,2‐dihydro‐2‐(4‐aminophenyl)‐4‐[4‐(4‐aminophenoxy)phenyl](2H)phthalazin‐1‐one and 1,2‐dihydro‐2‐(4‐aminophenyl)‐4‐[4‐(4‐aminophenoxy)‐3,5‐dimethylphenyl](2H) phthalazin‐1‐one, were successfully synthesized by readily available heterocyclic bisphenol‐like monomers through two steps in high yields. A series of novel poly(arylene ether amides)s containing the phthalazinone moiety with inherent viscosities of 1.16–1.67 dL/g were prepared by the direct polymerization of novel diamines and aromatic dicarboxylic acids using triphenyl phosphite and pyridine as condensing agents. The polymers were readily soluble in a variety of solvents such as N,N‐dimethylformamide, N,N‐dimethylacctamide, dimethyl sulfoxide, N‐methyl‐2‐pyrrolidone, and even in pyridine, chloroform and m‐cresol. The glass‐transition temperatures were in the range of 291–329 °C, and the temperatures for 5% weight loss in nitrogen were above 490 °C. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3489–3496, 2002     

Synthesis and characterization of novel aromatic polyamides derived from two heterocyclic diamines

Two diamines were synthesized as new aromatic monomers. A series of novel aromatic polyamides (aramids) were also synthesized by direct and indirect polycondensation of these diamines with various aromatic dicarboxylic acids. These aramids have inherent viscosities of 0.43-0.84 dl/g and were obtained in quantitative yield.     

Synthesis of polyamides from diols and diamines with liberation of H2

The amidation reaction based on catalytic coupling of alcohols with amines previously reported by us, using the pincer complexes 1 and 2 as catalysts, was applied to the generation of polyamides from nonactivated diols and diamines. A range of polymers was prepared, with M_n up to 26.9 kDa. Unlike the traditional syntheses of polyamides based on carboxylic acid derivatives, which require the use of toxic reagents and generate stoichiometric amounts of waste, this process generates only molecular hydrogen as byproduct. Both aromatic and aliphatic diols and diamines were used. Gel permeation chromatography measurements of the dimethylformamide‐soluble polymers and thermal studies of the polyamides were performed. Matrix assisted laser desorption/ionization time‐of‐flight (MALDI‐TOF) spectra are also reported. Thermogravimetric analyses studies indicate that the aromatic polyamides (with the exception of the pyridine‐based polyamide) are more thermally stable than the aliphatic ones. This general, environmentally benign method for the synthesis of polyamides is homogeneously catalyzed under neutral conditions by dearomatized ruthenium‐pincer complexes 1 and 2 and proceeds in 1,4‐dioxane under an inert atmosphere. Conditions for polyamidation in the absence of solvent are also reported, using the pincer complex 2 as catalyst. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and optical properties of asymmetric polyamides derived from cyclopropyl diacids and diamines

The polyamides were prepared from the dicarbonyl chloride of (+) (S)- or (?)(R)-trans-1,2-cyclopropanedicarboxylic acid (C3A) with either the dihydrochloride salt of (+)(S)- or (?)(R)-trans-1,2-diaminocyclopropane (C3B) or the dihydrobromide salt of (+)(S)- or (?)(R)-trans-1,2-bis(methylamino)cyclopropane (C3MB) by interfacial polycondensation. Several diamide model compounds composed of these monomers were also synthesized. The polyamides [poly(C3A-C3B)] derived from C3A and C3B have the capability of hydrogen bonding, while the polyamides [poly-(C3A-C3MB)] derived from C3A and C3MB do not. Poly(C3A-C3B) were insoluble in common organic solvents except strong acids. Poly(C3A-C3MB) were soluble in common organic solvents. Poly(C3A-C3B) had melting points higher than 300°C. Poly(C3A-C3MB) melted at 180–235°C. The ORD and CD study has shown that poly(+)C3A(+)C3B in methane sulfonic acid (MSA), 2,2,2-trifluoroethanol (TFE) (5 v % MSA), and tetramethylenesulfone (TMS) (5 v % MSA) exhibits a very strong Cotton effect or CD peak at 212–218 mμ, attributable to a component of the split π–π^* transition of the amide chromophores. Poly(+)C3A(+)C3MB in MSA and TFE (5 v % MSA) shows a strong Cotton effect or CD peak at 217–223 mμ and an intermediate Cotton effect or CD trough at 202–204 mμ as well as an intermediate Cotton effect or CD trough at 220–222 mμ and an intermediate Cotton effect or CD peak at 202–204 mμ in TFE and TMS. These peaks and troughs may be assigned to splitting of the π–π^* transition. The CD spectra of poly(+)C3A(+)C3MB in nonacidic media are quite different from those in acidic media: they are almost mirror images. The CD spectra in this transition induced by MSA suggests that a transition from a compact helix to another more extended helix with opposite handedness occurs similar to poly-L-proline I ? II. This transition may be explained by electrostatic repulsion between protonated amide groups. Viscosity data have shown that the conformation is changed to a highly extended from in acidic media. The polyamides and diamides derived from enantiomers exhibit mirror image spectra. Poly(+)C3A(+)C3B and poly(+)C3A(+)C3MB in every solvent studied exhibit a marked enhancement of the rotatory strength of ORD and CD with respect to the corresponding diamide models.     

NMR studies and conformations of asymmetric polyamides derived from cyclopropyl diacids and diamines

The synthesis and optical properties of the polyamides [poly(C3A˙C3B) and poly(C3A-C3MB)] derived from asymmetric trans-1,2-cyclopropanedicarboxylic acids (C3A), asymmetric trans-1,2-diaminocyclopropanes (C3B), and asymmetric trans-1,2-bis(methylamino) cyclopropanes (C3MB) were reported in the preceding article. This paper describes the NMR studies and conformations of the polyamides. The NMR studies of the polyamides and their diamide models have suggested that the polyamides have about a 90° torsional angle for NH (or CH₃) CH. This angle seems to be reasonable because of less steric interaction, especially for poly(+)C3A(+)C3MB. The N? CH₃ of the poly(+)C3A(+)C3MB in sulfuric acid-d₂ (D₂SO₄) is a singlet and is tentatively assigned to trans to the carbonyl oxygen of the amide group. In 2,2,2-trifluoroethanol-d₃ (TFE-d₃) and chloroform-d (CDCl₃) it is also a singlet and is tentatively assigned to cis. The overall results obtained suggest that poly(+)C3A(+)C3MB exists in a compact helical conformation in TFE and TMS, while some conformational transition to a highly extended helical form with opposite handedness is induced by the addition of MSA. Likewise, poly(+)C3A(+)C3B must exist in some ordered conformation in the solvents studied. Possible ordered conformations of the polyamides have been proposed based on the experimental results and some assumptions.     

Synthesis of wholly aromatic polysulfonamides from aromatic disulfonyl chlorides and aromatic diamines

Wholly aromatic polysulfonamides of high molecular weight were prepared by the solution poly-condensation of aromatic disulfonyl chlorides with aromatic diamines in tetramethylene sulfone and substituted pyridines as the acid acceptor. Polysulfonamides with inherent viscosities as high as 1.2 were readily obtained by initiating polycondensation at a temperature of 5–10°C to control the side reactions. The polycondensation was fairly fast and was completed in 10 min at 60°C. All the aromatic polysulfonamides dissolved in a wide range of solvents, including acetone and tetrahydrofuran. These polymers were less thermally stable than the corresponding aromatic polyamides.     

Aromatic polyamides. V. A general synthesis of polyamides from aromatic diacids and aromatic diamines in sulfur trioxide

The reaction of terephthalic acid (TA) and para-phenylenediamine sulfate (PPD-S) in sulfur trioxide to form anisotropic, sulfonated poly(p-phenyleneterephthalamide) (SPT) dopes was reported in Part IV of this series. We have found now that the TA/PPD-S polymerization is only one example of a more general polyamide condensation reaction of aromatic diamines and aromatic diacids. Sulfonation of the aromatic diamine ring during TA/PPD-S polymerization in SO₃ was a major side reaction. Sulfonation was reduced or eliminated by aromatic diamine ring substitution with unreactive substituents, particularly chlorine and fluorine. Polymerization of 2,3,5,6-tetrafluoro-phenylenediamine with TA in SO₃ at 80°C (18% concentration) produced unsulfonated poly(tetrafluoro-para-phenyleneterephthalamide) (F-PPT) with an inherent viscosity of 2.2. The halogenated, all-para aromatic polymers formed highly anisotropic (liquid crystalline) dopes. Monomers that formed polymers in which the chain bond angle deviated from 180° (e.g., meta-oriented monomers) yielded only isotropic polymer solutions. The mechanism and rate of diamine–diacid reactivity in SO₃ was related to diamine basicity. Whereas the less basic aromatic diamines (as sulfates) polymerized with aromatic diacids in SO₃, the more basic aliphatic diamines (as sulfates) would not. Aliphatic, cycloaliphatic, and aryl-aliphatic diacids were degraded by or reacted with the solvent (SO₃). Thermogravimetric analyses of F-PPT and monosulfonated poly(chloro-para-phenyleneterephthalamide) at 20°C/min showed weight loss only above 380 and 370°C, respectively.     

Synthesis of polyamides from active 1-benzotriazolyl diesters and diamines under mild conditions

The effect of the solvent on the inherent viscosity of polyamides was investigated in the polycondensation of new active 1-benzotriazolyl diesters, such as 1,1′-(adipolydioxy)bisbenzotriazole and 1,1′-(isophthaloyldioxy)bisbenzotriazole, with diamines. The preferred polymerization media were polar aprotic solvents, including N-methyl-2-pyrrolidone and hexamethylphosphoramide. The solution polycondensation at room temperature afforded a series of polyamides having inherent viscosities as high as 1.8 from both aliphatic and aromatic diamines. The 1-benzotriazolyl diesters were more reactive than di(2,4-dinitrophenyl) isophthalate toward diamines. Prior to polymer synthesis, the aminolysis of some active monoesters was carried out as a model compound study.     

Synthesis of polyamides from active 2-benzothiazolyl diesters and diamines under mild conditions

2-Benzothiazolyl benzoate as a model compound was successfully synthesized from the benzoylation of 2-benzothiazolone under kinetically controlled conditions. The aminolysis of 2-benzothiazolyl benzoate afforded excellent yields of N-substituted benzamides at room temperature in a short reaction time. Solution polycondensations of new active diesters, di-2-benzothiazolyl isophthalate and di-2-benzothiazolyl terephthalate, with aliphatic and aromatic diamines, took place rapidly even at room temperature and yielded polyamides with high molecular weight. The high reactivity of 2-benzothiazolyl benzoate was discussed in relation to intramolecular general base catalysis and the tautomeric effect of the benzothiazolone moiety.     

Synthesis of polyamides from active 2-benzothiazolyl dithiolesters and diamines under mild conditions

Novel examples were presented of the use in polyamide synthesis of active 2-benzothiazolyl dithiolesters for which aminolysis is assisted by a neighboring group. Solution polycondensation of new dithiolesters, 2,2′-(adipoyldithio)bisbenzothiazole and 2,2′-(isophtahloyldithio)bisbenzothiazole, with both aliphatic and aromatic diamines in polar aprotic solvents (N-methyl-2-pyrrolidone and hexamethylphosphoramide) took place rapidly at room temperature yielding polyamides with high molecular weight. The interfacial polycondensation in a chloroform–water system was also successful for polyamide formation. S,S′-Di-p-nitrophenyl dithioisophthalate reacted much more slowly toward diamines than the 2-benzothiazolyl dithiolesters. Prior to polymer synthesis, the aminolysis of active monothiolesters was carried out as a model compound study.