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.     

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.     

New poly(amide–imide) syntheses. XXI. Synthesis and properties of aromatic poly(amide–imide)s based on 2,6-bis(4-trimellitimidophenoxy)naphthalene and aromatic diamines

A novel polymer-forming diimide–diacid, 2,6-bis(4-trimellitimidophenoxy)naphthalene, was prepared by the condensation reaction of 2,6-bis(4-aminophenoxy)naphthalene with trimellitic anhydride (TMA). A series of novel aromatic poly(amide–imide)s containing 2,6-bis(phenoxy)naphthalene units were prepared by the direct polycondensation of the diimide–diacid with various aromatic diamines using triphenyl phosphite (TPP) in N-methyl-2-pyrrolidone (NMP)/pyridine solution containing dissolved calcium chloride. Thirteen of the obtained polymers had inherent viscosities above 1.01 dL/g and up to 2.30 dL/g. Most of polymers were soluble in polar solvents such as DMAc and could be cast from their DMAc solutions into transparent, flexible, and tough films. These films had tensile strengths of 79–117 MPa, elongation-at-break of 7–61%, and initial moduli of 2.2–3.0 GPa. The wide-angle X-ray diffraction revealed that some polymers are partially crystalline. The glass transition temperatures of some polymers could be determined with the help of differential scanning calorimetry (DSC) traces, which were recorded in the range 232–300°C. All the poly(amide–imide)s exhibited no appreciable decomposition below 450°C, and their 10% weight loss temperatures were recorded in the range 511–577°C in nitrogen and 497–601°C in air. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 919–927, 1998     

Synthesis and properties of novel aromatic polyamides derived from 1,5-bis(4-aminophenoxy)naphthalene and aromatic dicarboxylic acids

A new bis(phenoxy)naphthalene-containing diamine, 1,5-bis(4-aminophenoxy)naphthalene, was synthesized in two steps from the condensation of 1,5-dihydroxy-naphthalene with p-chloronitrobenzene in the presence of potassium carbonate, giving 1,5-bis(4-nitrophenoxy)naphthalene, followed by hydrazine hydrate/Pd? C reduction. A series of polyamides and copolyamides were synthesized by the direct polycondensation of the diamine with various aromatic dicarboxylic acids or with mixed dicarboxylic acids in N-methyl-2-pyrrolidone (NMP) using triphenyl phosphite and pyridine as condensing agents. The polymers having inherent viscosity of 0.81–1.25 dL/g were obtained in quantitative yield. Most of the polymers were generally soluble in aprotic solvent such as N,N-dimethylacetamide, N-methyl-2-pyrrolidone, etc. The polymers derived from rigid dicarboxylic acids such as terephthalic acid, naphthalene dicarboxylic acid, and 4,4′-biphenyldicarboxylic acid exhibited crystalline patterns. Glass transition temperatures of polymers were in the range of 230–360°C, and 10% weight loss temperatures in nitrogen and air were above 492 and 470°C, respectively. © 1993 John Wiley & Sons, Inc.     

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 properties of poly(amide-imide)s based on the diimide-diacid condensed from 2,2′- bis(4-aminophenoxy)biphenyl and trimellitic anhydride

A new dicarboxylic acid having a kinked structure was synthesized from the condensation of 2,2′-bis(4-aminophenoxy)biphenyl and trimellitic anhydride. A series of biphenyl-2,2′-diyl-containing aromatic poly(amide-imide)s having inherent viscosities of 0.23–0.94 dL/g was prepared by the triphenyl phosphite activated polycondensation from the diimide-diacid II 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 a variety of organic solvents including NMP and N,N-dimethylacetamide (DMAc). Transparent, flexible, and tough films of these polymers could be cast from DMAc or NMP solutions. The glass transition temperatures of these polymers were in the range of 227–261°C and the 10% weight loss temperatures were above 520°C in nitrogen. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1169–1177, 1998     

Synthesis and properties of new polyimides derived from 1,5-bis(4-aminophenoxy)naphthalene and aromatic tetracarboxylic dianhydrides

Novel aromatic polyimides containing bis(phenoxy)naphthalene units were synthesized from 1,5-bis(4-aminophenoxy)naphthalene (APN) and various aromatic tetracarboxylic dianhydrides by the usual two-step procedure that included ring-opening polyaddition in a polar solvent such as N,N-dimethylacetamide (DMAc) to give poly(amic acid)s, followed by cyclodehydration to polyimides. The poly(amic acid)s had inherent viscosities between 0.72 and 1.94 dL/g, depending on the tetracarboxylic dianhydrides used. Excepting the polyimide IVb obtained from 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA), all other polyimides formed brown, flexible, and tough films by casting from the poly(amic acid) solutions. The polyimide synthesized from BPDA was characterized as semicrystalline, whereas the other polyimides showed amorphous patterns as shown by the x-ray diffraction studies. Tensile strength, initial moduli, and elongation at break of the APN-based polyimide films ranged from 105–135 MPa, 1.92–2.50 GPa, and 6–7%, respectively. These polyimides had glass transition temperatures between 228 and 317°C. Thermal analyses indicated that these polymers were fairly stable, and the 10% weight loss temperatures by TGA were recorded in the range of 543–574°C in nitrogen and 540–566°C in air atmosphere, respectively. © 1993 John Wiley & Sons, Inc.     

Synthesis and properties of aromatic polyamides derived from 2,6-bis(4-aminophenoxy)naphthalene and various aromatic dicarboxylic acids

2,6-Bis(4-aminophenoxy)naphthalene (2,6-BAPON) was synthesized in two steps from the condensation of 2,6-dihydroxynaphthalene with p-chloronitrobenzene in the presence of potassium carbonate, giving 2,6-bis(4-nitrophenoxy)naphthalene, followed by hydrazine hydrate/Pd—C reduction. A series of new polyamides were synthesized by the direct polycondensation of 2,6-BAPON with various aromatic dicarboxylic acids in the N-methyl-2-pyrrolidone (NMP) solution containing dissolved metal salts such as CaCl₂ or LiCl using triphenyl phosphite and pyridine as condensing agents. The polymers were obtained in quantitative yields with inherent viscosities of 0.62–2.50 dL/g. Most of the polymers were soluble in aprotic dipolar solvents such as N,N-dimethylacetamide (DMAc) and NMP, and they could be solution cast into transparent, flexible, and tough films. The casting films had yield strengths of 84–105 MPa, tensile strengths of 68–95 MPa, elongations at break of 8–36%, and tensile moduli of 1.4–2.1 GPa. The glass transition temperatures of the polyamides were in the range 155–225°C, and their 10% weight loss temperatures were above 505°C in nitrogen and above 474°C in air. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2147–2156, 1997     

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.     

Synthesis and properties of aromatic polyamides derived from 1,7-bis(4-aminophenoxy)naphthalene and various aromatic dicarboxylic acids

A series of novel bis(phenoxy)naphthalene-containing polyamides having inherent viscosity up to 2.02 dL/g were synthesized by the direct polycondensation of the diamine 1,7-bis(4-aminophenoxy)naphthalene with various aromatic dicarboxylic acids in N-methyl-2-pyrrolidone (NMP) using triphenyl phosphite and pyridine as condensing agents. Most of the polyamides could be readily dissolved in polar aprotic solvents such as N,N-dimethylacetamide and NMP, and could be solution-cast into transparent, flexible, and tough films. These polymers had glass transition temperatures in the range of 139–263°C, and 10% weight loss temperatures in nitrogen and air were above 499 and 484°C, respectively. © 1996 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 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.     

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.     

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.     

Synthesis and characterization of new poly(amide–imide)s from 1,4-bis(4-trimellitimidophenoxy)-2-tert-butylbenzene with various diamines

New poly(amide–imide)s were prepared from a diimide–dicarboxylic acid, 1,4-bis(4-trimellitimidophenoxy)-2-tert-butylbenzene ( BTTB ), with various diamines by the direct polycondensation in N-methyl-2-pyrrolidinone (NMP) using triphenyl phosphite and pyridine as condensing agents. The new diimide–dicarboxylic acid BTTB containing an ether linkage and tert-butyl substituent was synthesized by the condensation reaction of 1,4-bis(4-aminophenoxy)-2-tert-butylbenzene with trimellitic anhydride. All the polymers were obtained in quantitative yields with inherent viscosities of 0.62–1.06 dL g⁻¹. The polymers were amorphous, and most of them were readily soluble in aprotic polar solvents such as NMP, N,N-dimethylacetamide (DMAc), and N,N-dimethylformamide (DMF), as well as in less polar solvents such as dimethyl sulfoxide (DMSO), m-cresol, pyridine, and γ-butyrolactone, and also even in tetrahydrofuran. The glass transition temperatures of the polymers were determined by DSC method, and they were in the range of 238–279°C. These polymers were stable up to 408–449°C in air and 451–483°C in nitrogen and lose 10% weight in the range of 479–525°C in air and 480–528°C in nitrogen atmosphere. The polymer films had a tensile strength range of 71–115 MPa, an elongation at break range of 4–14%, and a tensile modulus range of 2.3–3.1 GPa. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2301–2307, 1998     

Synthesis and properties of polyimides,polyamides and poly(amide-imide)s from ether diamine having the spirobichroman structure

A novel spirobichroman unit containing dietheramine, 6,6′-bis(4-aminophenoxy)-4,4,4′,4′,7,7′-hexamethyl-2,2′-spirobichroman ( 3 ), was prepared by the nucleophilic substitution of 6,6′-dihydroxy-4,4,4′,4′,7,7′-hexamethyl-2,2′-spirobichroman with p-chloronitrobenzene in the presence of K₂CO₃ followed by hydrazine catalytic reduction of the intermediate dinitro compound. A series of polyimides were synthesized from diamine 3 and various aromatic dianhydrides by a conventional two-stage procedure through the formation of poly(amic-acid)s followed by thermal imidization. The intermediate poly(amic-acid)s had inherent viscosities of 1.00–2.78 dL/g. All the poly-(amic-acid)s could be thermally cyclodehydrated into flexible and tough polyimide films, and some polyimides were soluble in polar solvents such as N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), and N,N-dimethylformamide (DMF). These polyimides had glass transition temperatures (T_g) in the range of 236–256°C, and 10% weight loss occurred up to 450°C. Furthermore, a series of polyamides and poly(amide-imide)s with inherent viscosities of 0.71–2.29 dL/g were prepared by direct polycondensation of the diamine 3 with various aromatic dicarboxylic acids and imide ring-containing dicarboxylic acids by means of triphenyl phosphite and pyridine. All the polyamides and poly(amide-imide)s were readily soluble in polar solvents such as DMAc, and tough and flexible films could be cast from their DMAc solutions. These polymers had glass transition temperatures in the range of 137–228°C and 10% weight loss temperatures in the range of 419–443°C in air and 404–436°C in nitrogen, respectively. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1487–1497, 1997     

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.     

Preparation and properties of aromatic polyamides from 1,4-bis(p-carboxyphenoxy)naphthyl and aromatic diamines

A new aromatic dicarboxylic acid, 1,4-bis (p-carboxyphenoxy)naphthyl ( 3 ), was synthesized by the reaction of p-fluorobenzonitrile with 1,4-naphthalenediol, followed by hydrolysis. Aromatic polyamides having inherent viscosities of 1.27–2.22 dL/g were prepared by the triphenyl phosphite activated polycondensation of diacid 3 with various aromatic diamines. Most of the resulting polymers showed an amorphous nature and were readily soluble in a variety of organic solvents including N,N-dimethyl-acetamide (DMAc), N-methyl-2-pyrrolidone (NMP), and m-cresol. Transparent, tough, and flexible films of these polymers could be cast from the DMAc or NMP solutions. The cast films had tensile strengths ranging from 64–104 MPa, elongations-at-break from 6 to 10%, and initial moduli from 1.52 to 2.14 GPa. These polyamides had glass transition temperatures in the range of 195 to 240°C. Almost all polymers were thermally stable up to 400°C, with 10% weight loss being recorded above 480°C in air and nitrogen atmospheres. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2273–2280, 1997     

Preparation and properties of aromatic polyimides from 2,2′-bis(p-aminophenoxy)biphenyl or 2,2′-bis)p-aminophenoxy)-1,1′-binaphthyl and aromatic tetracarboxylic dianhydrides

New aromatic polyimides containing a biphenyl-2,2′-diyl or 1,1′-binaphthyl-2,2′-diyl unit were prepared by a conventional two-step method starting from 2,2′-bis(p-aminophenoxy) biphenyl or 2,2′-bis(p-aminophenoxy)-1,1′-binaphthyl and aromatic tetracarboxylic dianhydrides. The polyimides having inherent viscosities of 0.69–0.99 and 0.51–0.59 dL/g, respectively, were obtained. Some of these polymers were readily soluble in a variety of organic solvents including N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide, and pyridine. Transparent, flexible, and pale yellow to brown films of these polymers could be cast from the DMAc or NMP polyamic acid solutions. These aromatic polyimides containing biphenyl and binaphthyl units had glass transition temperatures in the range of 200–235 and 286–358°C, respectively. They began to lose weight around 380°C, with 10% weight loss being recorded at about 470°C in air. © 1993 John Wiley & Sons, Inc.     

Soluble poly(amide–imide)s prepared by one‐pot solution condensation

A new one‐pot procedure for imide–acid monomer synthesis and polymerization is reported for four new poly(amide–imide)s. Bisphenol A dianhydride (BPADA) was reacted with twice the molar amount of 3‐aminobenzoic acid (3ABA) or 3‐amino‐4‐methylbenzoic acid (3A4MBA) in 1‐methyl‐2‐pyrrolidinone (NMP) and toluene mixture, and the amic acid intermediates cyclized in solution to give two diimide‐containing dicarboxylic acid monomers. Without isolation, the diacid monomers were then polymerized with either 1,3‐diaminomesitylene (DAM) or 1,5‐diaminonaphthalene (1,5NAPda) using triphenyl phosphite‐activation to give a series of four soluble poly(amide–imide)s, PAI. Isolation and purification of the dicarboxylic acid monomers was not necessary for formation of high molecular weight polymers as indicated by intrinsic viscosities of 0.64–1.04 dL/g determined in N,N‐dimethylacetamide (DMAc). All of the PAI were soluble in polar aprotic solvents such as NMP, DMAc, and dimethyl sulfoxide (DMSO). Glass transition temperatures ranged from 243 to 279°C by DSC, and 5% weight loss temperatures were above 400°C in both air and nitrogen. Flexible films cast from DMAc were light yellow, transparent, and tough. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1183–1188, 1999