Synthesis and properties of aromatic polyamides derived from 1,6-bis(4-aminophenoxy)naphthalene and aromatic dicarboxylic acids

A new bis(phenoxy)naphthalene-containing diamine, 1,6-bis(4-aminophenoxy)naphthalene, was synthesized in two steps from the condensation of 1,6-dihydroxynaphthalene with p-chloronitrobenzene in the presence of potassium carbonate, giving 1,6-bis(4-nitrophenoxv)naphthalene, followed by hydrazine hydrate/Pd—C reduction. A series of polyamides were synthesized by the direct polycondensation of the diamine with various aromatic dicarboxylic acids in the N-methyl-2-pyrrolidone (NMP) solution containing dissolved metal salts such as CaCl₂ or LiBr using triphenyl phosphite and pyridine as condensing agents. The polymers were obtained in quantitative yield with inherent viscosities of 0.78–3.72 dL/g. Most of the polymers were soluble in aprotic solvents such as N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), NMP, and they could be solution-cast into transparent, flexible and tough films. The casting films had tensile strength of 102–175 MPa, elongation at break of 8–42%, and tensile modulus of 2.4–3.8 GPa. The polymers derived from rigid dicarboxylic acids such as terephthalic acid and 4,4′-biphenyldicarboxylic acid exhibited some crystalline characteristics. The glass transition temperatures of the polyamides were in the range of 238–337°C, and their 10% weight loss temperatures were above 487°C in nitrogen and above 438°C in air. © 1995 John Wiley & Sons, Inc.     

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.     

Synthesis and properties of aromatic polyamides derived from 1,2-bis(4-aminophenoxy)benzene and aromatic dicarboxylic acids

1,2-Bis(4-aminophenoxy)benzene was synthesized in two steps by the preparation of 1,2-bis(4-itrophenoxy)benzene from 1,2-dihydroxybenzene (catechol) and p-chloronitrobenzene and subsequent reduction with a 10% Pd-C catalyst and hydrazine hydrate. Aromatic polyamides with an inherent viscosity in the range of 1.08–2.00 dL/g were prepared by the direct polycondensation of this diamine with various aromatic dicarboxylic acids in N-methyl-2-pyrrolidone (NMP) using triphenyl phosphite and pyridine as condensing agents. Most of the polymers formed were soluble in aprotic solvents such as NMP and N,N-methylacetamide (DMAc), and afforded transparent, flexible, and tough films upon casting from DMAc solutions. Most of the cast films showed obvious yield points in their stress-strain curves and had tensile strength among 64–89 MPa, elongation at break among 5–23%, and initial modulus in 1.7–2.5 GPa. The glass transition temperatures (T_g) of these polymers were in the range of 207–278°C, and the 10% weight loss temperatures were recorded above 475°C in nitrogen and above 452°C in air. © 1995 John Wiley & Sons, Inc.     

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.     

New poly(amide-imide)s syntheses. VII. Preparation and properties of poly(amide-imide)s derived from 1,5-bis(4-aminophenoxy) naphthalene,trimellitic anhydride,and various aromatic diamines

New bis(phenoxy)naphthalene-containing poly(amide-imide)s having an inherent viscosity in the range of 0.62–1.09 dL/g were prepared by the direct polycondensation of 1,5-bis(4-trimellitimidophenoxy) naphthalene ( I ) and various aromatic diamines using triphenyl phosphite and pyridine as condensing agents in N-methyl-2-pyrrolidone (NMP) in the presence of calcium chloride. The diimide-diacid (I) was prepared by the condensation of 1,5-bis(4-aminophenoxy) naphthalene and trimellitic anhydride. Most of the polymers were soluble in aprotic solvents such as NMP and N,N-dimethylacetamide (DMAc), and afforded transparent, flexible and tough films upon casting from DMAc solutions. Measurements of wide-angle X-ray diffraction revealed that those polymers containing p-phenylene or oxyphenylene groups were characterized as crystalline polymers. Tensile strength and initial moduli of the polymer films ranged from 61–86 MPa and 1.83–2.21 GPa, respectively. Glass transition temperatures of the polymers were in the range of 231–340°C. The melting points of the crystalline polymers ranged from 375–430°C. The 10% weight loss temperatures were above 512°C in nitrogen and 481°C in air. © 1993 John Wiley & Sons, Inc.     

Synthesis and Properties of Aromatic Poly(Ether Sulfone)s and Poly(Etherketone)s Containing Naphthalene or Quinoline Units,and Methyl-Substituted Biphenyl-4,4′-Diols

Abstract

A series of poly(ether sulfone)s and poly(ether ketone)s were synthesized from combinations of 1,5- and 2,6-bis(4-fluorosulfonyl)naphthalene, 2,6-bis(4-fluorobenzoyl)naphthalene, and 2,6-bis(4-fluorobenzoyl)quinoline with 3,3′,5,5′-tetramethylbiphenyl-4,4′-diol and 2,2′,3,3′,5,5′-hexamethylbiphenyl-4,4′-diol. The polycondensations proceeded quantitatively in diphenylsulfone in the presence of anhydrous potassium carbonate to afford polymers with inherent viscosities between 0.40 and 1.28 dL/g measured in N-methyl-2-pyrrolidone or concentrated sulfuric acid. The tetramethyl- and hexamethyl-substituted aromatic polyethers exhibited good thermal stability, did not decompose below 330°C in both air and nitrogen atmospheres, and had higher glass transition temperatures than the corresponding unsubstituted polymers. The methylsubstituted poly(ether sulfone)s and poly(ether ketone)s showed good solubility in such common organic solvents as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, tetrahydrofuran, chloroform, and 1,4-dioxane.     

Syntheses and properties of aromatic polyamides and polyimides based on N-phenyl-3,3-bis[4-(p-aminophenoxy) phenyl] phthalimidine

N-Phenyl-3,3-Bis[4-(p-aminophenoxy)phenyl] phthalimidine ( II ) was used as a monomer with various aromatic dicarboxylic acids and tetracarboxylic dianhydrides to synthesize polyamides and polyimides, respectively. The diamine II was derived by a nucleophilic substitution of N-phenyl-3,3-bis(4-hydroxyphenyl) phthalimidine with p-chloronitrobenzene in the presence of K₂CO₃ and then hydro-reduced. Polyamides IV _a-g having inherent viscosities of 0.55–1.64 dL/g were prepared by the direct polycondensation of the diamine II with various aromatic diacids using triphenyl phosphite and pyridine as condensing agents. All the aromatic polyamides were amorphous and readily soluble in various polar solvents such as N,N-dimethylacetamide (DMAc), N,N-dimethylformamide, dimethylsulfoxide, and N-methyl-2-pyrrolidone (NMP). Transparent and flexible films of these polymers could be cast from the DMAc solutions. These aromatic polyamides had glass transition temperatures in the range of 293–319°C and 10% weight loss occurred up to 480°C. The polyimides were synthesized from diamine II and various aromatic dianhydrides via the two-stage procedure that included ring-opening polyaddition in DMAc to give poly(amic acid)s, followed by thermal or chemical conversion to polyimides. Most of the aromatic polyimides obtained by chemical cyclization were found to be soluble in NMP, m-cresol, and o-chlorophenol. These polyimides showed almost no weight loss up to 500°C in air or nitrogen atmosphere. © 1994 John Wiley & Sons, Inc.     

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 aromatic polyamides from 2,2′-bis(p-carboxyphenoxy) biphenyl or 2,2′-bis(p-carboxyphenoxy)-1,1′-binaphthyl and aromatic diamines

New aromatic dicarboxylic acids having kink and crank structures, 2,2′-bis(p-carboxyphenoxy) biphenyl and 2,2′-bis(p-carboxyphenoxy)-1,1′-binaphthyl, were synthesized by the reaction of p-fluorobenzonitrile with biphenyl-2,2′-diol and 2,2′-dihydroxy-1,1′-binaphthyl, respectively, followed by hydrolysis. Biphenyl-2,2′-diyl-and 1,1′-binaphthyl-2,2′-diyl-containing aromatic polyamides having inherent viscosities of 0.58–1.46 dL/g and 0.63–1.30 dL/g, respectively, were obtained by the low-temperature solution polycondensation of the corresponding diacid chlorides with aromatic diamines. These polymers were readily soluble in a variety of organic solvents including N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide, m-cresol, and pyridine. Transparent, pale yellow, and flexible films of these polymers could be cast from the DMAc or NMP solutions. These aromatic polyamides containing biphenyl and binaphthyl units had glass transition temperatures in the range of 210–272 and 260–315°C, respectively. They began to lose weight around 380°C, with 10% weight loss being recorded at about 450°C in air. © 1993 John Wiley & Sons, Inc.     

Polyimides from 1,5-bis(4-amino-2-trifluoromethylphenoxy)naphthalene and aromatic tetracarboxylic dianhydrides

A new trifluoromethylated bis(ether amine), 1,5-bis(4-amino-2-trifluoromethylphenoxy)naphthalene, was synthesized in two steps starting from 1,5-dihydroxynaphthalene and 2-chloro-5-nitrobenzotrifluoride via nucleophilic aromatic substitution and catalytic reduction. A series of novel fluorinated polyimides with moderate to high molecular weights were synthesized from the diamine with various aromatic tetracarboxylic dianhydrides using a conventional two-stage process. All polyimides could afford flexible and tough films and most of them were soluble in strong polar solvents such as N-methyl-2-pyrrolidone (NMP) and N,N-dimethylacetamide (DMAc). The polyimides showed glass-transition temperatures (T_g) in the range of 253-315 °C (by DSC) and softening temperatures (T_s) in the range of 250-300 °C (by TMA). Decomposition temperatures for 5% weight loss all occurred above 500 °C in both air and nitrogen atmospheres. The dielectric constants of these polymers ranged from 3.17 to 3.64 at 1 MHz. The properties of these fluorinated polyimides were also compared with those of polyimides prepared from 1,5-bis(4-aminophenoxy)naphthalene with the same dianhydrides.     

Syntheses and properties of aromatic polyamides and polyimides derived from 9,9-bis[4-(p-aminophenoxy)phenyl]fluorene

9,9-Bis[4-(p-aminophenoxy)phenyl]fluorene ( II ) was used as a monomer with various aromatic dicarboxylic acids and tetracarboxylic dianhydrides to synthesize polyamides and polyimides, respectively. The diamine II was derived by a nucleophilic substitution of 9,9-bis(4-hydroxyphenyl)fluorene with p-chloronitrobenzene in the presence of K₂CO₃ and then hydro-reduced. Polyamides IV _a-g having inherent viscosities of 0.73–1.39 dL/g were prepared by the direct polycondensation of the diamine II with various aromatic diacids using triphenyl phosphite and pyridine as condensing agents. All the aromatic polyamides were amorphous and readily soluble in various polar solvents such as N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, and N-methyl-2-pyrrolidone. Transparent and flexible films of these polymers could be cast from the DMAc solutions. These aromatic polyamides had glass transition temperatures in the range of 283–309°C and 10% weight loss occurred up to 460°C. The polyimides were synthesized from diamine II and various aromatic dianhydrides via the two-stage procedure that included ring-opening poly-addition in DMAc to give poly(amic acid)s, followed by thermal or chemical conversion to polyimides. The poly(amic acid)s had inherent viscosities of 0.62–1.78 dL/g, depending on the dianhydrides. Most of the aromatic polyimides obtained by chemical cyclization were found to be soluble in NMP. These polyimides showed almost no weight loss up to 500°C in air or nitrogen atmosphere. © 1993 John Wiley & Sons, Inc.     

Preparation and properties of aromatic polyamides from 2,2′-bis(p-aminophenoxy) biphenyl or 2,2′-bis(p-aminophenoxy)-1,1′-binaphthyl and aromatic dicarboxylic acids

New aromatic diamines having kink and crank structures, 2,2′-bis(p-aminophenoxy)biphenyl and 2,2′-bis(p-aminophenoxy)-1,1′-binaphthyl, were synthesized by the reaction of p-fluoronitrobenzene with biphenyl-2,2′-diol and 2,2′-dihydroxy-1,1′-binaphthyl, respectively, followed by catalytic reduction. Biphenyl-2,2′-diyl- and 1,1′-binaphthyl-2,2′-diyl-containing aromatic polyamides having inherent viscosities of 0.44–1.18 and 0.26–0.88 dL/g, respectively, were obtained either by the direct polycondensation or low-temperature solution polycondensation of the diamines with aromatic dicarboxylic acids (or diacid chlorides). These polymers were readily soluble in a variety of organic solvents including N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide, m-cresol, and pyridine. Transparent, pale yellow, and flexible films of these polymers could be cast from the DMAc or NMP solutions. These aromatic polyamides containing biphenyl and binaphthyl units had glass transition temperatures in the range of 215–255 and 266–303°C, respectively. They began to lose weight at ca. 380°C, with 10% weight loss being recorded at about 470°C in air. © 1993 John Wiley & Sons, Inc.     

Synthesis and characterization of novel polyarylates from 2,5-bis(4-hydroxyphenyl)-3,4-diphenylpyrrole and various aromatic dicarboxylic acids

A new tetraphenylated heterocylic diol, 2,5-bis(4-hydroxyphenyl)-3,4-diphenylpyrrole, was synthesized in three steps starting from 4-methoxydeoxybenzoin. The tetraphenylpyrrole-containing polyarylates having inherent viscosities of 0.28–0.88 dL/g were prepared from the diol and various aromatic dicarboxylic acid chlorides by both phase transfer catalyzed two-phase polycondensation and high temperature solution polymerization methods. All the polyarylates were semi-crystalline, and were readily soluble in a variety of solvents including N-methyl-2-pyrrolidone, m cresol, pyridine, and 1,4-dioxane. These polymers had glass transition temperatures in the range of 223–279°C, with no weight loss below 400°C in both air and nitrogen atmospheres. © 1994 John Wiley & Sons, Inc.     

Synthesis of polypyrimidoquinazolinetetraones from N,N′-bis(mesyloxy)pyromellitimide and aromatic diamines

A novel class of polypyrimidoquinazolinetetraones was synthesized by the polymerization of N,N′-bis(mesyloxy)pyromellitimide with aromatic diamines in N-methyl-2-pyrrolidone in the presence of triethylamine as an acid acceptor. The polymerization proceeded probably through the formation of ring-opened adducts, followed by elimination and rearrangement yielding polyamide-isocyanates, which in turn were cyclized to give polypyrimidoquinazolinetetraones. These polymers, which were soluble in strong acids, had inherent viscosities in the range of 0.17–0.27. Thermogravimetric analyses indicated that they began to decompose at around 450°C in air.     

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.     

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 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.     

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.     

New poly(amide-imide)s syntheses. VIII. Preparation and properties of poly (amide-imide)s derived from 2,3-bis(4-aminophenoxy)naphthalene,trimellitic anhydride,and various aromatic diamines

The new polymer-forming diimide-diacid, 2,3-bis(4-trimellitimidophenoxy) naphthalene (I), was readily obtained by the condensation reaction of 2,3-bis (4-aminophenoxy) naphthalene with trimellitic anhydride. A series of novel aromatic poly (amide-imide)s were prepared by the direct polycondensation of diimide-diacid I with various aromatic diamines using triphenyl phosphite in N-methyl-2-pyrrolidone (NMP)/pyridine solution containing dissolved calcium chloride. The resultant polymers have inherent viscosities in the range of 0.65–1.02 dL/g at 30°C in N, N-dimethylacetamide. These polymers were readily soluble in various organic solvents and could be cast into transparent, tough, and flexible films. Their casting films showed tensile strength at break up to 86 MPa, elongation to break of 5–9%, and initial moduli up to 2.35 GPa. The wide-angle X-ray diffraction revealed that those polymers containing p-phenylene or p-oxyphenylene group are partially crystalline, and the other polymers are evidenced as amorphous patterns. These polymers show a glass transition in the range of 213–290°C in their differential scanning calorimetry (DSC) traces. The thermal stability of the polymers was evaluated by thermogravimetry analysis, which showed the 10% weight-loss temperatures in the range of 508–565°C in nitrogen and 480–529°C in air atmosphere. © 1994 John Wiley & Sons, Inc.     

Preparation and properties of aromatic polyamides from 5-t-butylisophthalic acid and various aromatic diamines

Aromatic polyamides (aramids) having pendant t-butyl group were synthesized by the direct polycondensation of 5-t-butylisophthalic acid with various aromatic diamines in N-methyl-2-pyrrolidone (NMP) using triphenyl phosphite and pyridine as condensing agents. The aramids having inherent viscosities of 0.6–2.4 dL/g were obtained in quantitative yields. These polymers were readily soluble in various solvents such as NMP,N,N-dimethylacetamide, dimethyl sulfoxide, and pyridine, and gave transparent, tough and flexible films by casting from the NMP solutions. The aramids had glass transition temperatures between 250 and 330°C, and started to lose weight around 350°C, with 10% weight loss being recorded at about 450°C in air.