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 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.     

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     

Synthesis and properties of new polyamides derived from 1,4-bis(4-aminophenoxy)-2,5-di-tert-butylbenzene and aromatic dicarboxylic acids

The diamine 1,4-bis(4-aminophenoxy)-2,5-di-tert-butylbenzene, containing symmetric, bulky di-tert-butyl substituents and a flexible ether unit, was synthesized and used to prepare a series of polyamides by the direct polycondensation with various aromatic dicarboxylic acids in N-methyl-2-pyrrolidinone (NMP) using triphenyl phosphite and pyridine as condensing agents. All the polymers were obtained in quantitative yields with inherent viscosities of 0.32–1.27 dL g⁻¹. Most of these polyamides, except II _a , II _d , and II _e , showed an amorphous nature and dissolved in polar solvents and less polar solvents. Polyamides derived from 4,4′-sulfonyldibenzoic acid, 4,4′-(hexafluoro-isopropylidene)dibenzoic acid, and 5-nitroisophthalic acid were even soluble in a common organic solvent such as THF. Most polyamide films could be obtained by casting from their N,N-dimethylacetamide (DMAc) solutions. The polyamide films had a tensile strength range of 49–78 MPa, an elongation range at break of 3–5%, and a tensile modulus range of 1.57–2.01 GPa. These polyamides had glass transition temperatures ranging between 253 and 276°C, and 10% mass loss temperatures were recorded in the range 402–466°C in nitrogen atmosphere. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1069–1074, 1998     

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 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.     

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 polyimides derived from 1,6-bis(4-aminophenoxy)naphthalene and aromatic tetracarboxylic dianhydrides

1,6-Bis(4-aminophenoxy)naphthalene ( I ) was used as a monomer with various aromatic tetracarboxylic dianhydrides to synthesize polyimides via a conventional two-stage procedure that included ring-opening polyaddition in a polar solvent such as N,N-dimethylacetamide (DMAc) to give poly(amic acid)s, followed by thermal cyclodehydration to polyimides. The diamine ( I ) was prepared through the nucleophilic displacement of 1,6-dihydroxynaphthal-ene with p-chloronitrobenzene in the presence of K₂CO₃, followed by catalytic reduction. Depending on the dianhydrides used, the poly(amic acid)s obtained had inherent viscosities of 0.73–2.31 dL/g. All the poly(amic acid)s could be solution cast and thermally converted into transparent, flexible, and tough polyimide films. The polyimide films had a tensile modulus range of 1.53–1.84 GPa, a tensile strength range of 95–126 MPa, and an elongation range at break of 9–16%. The polyimide derived from 4,4′-sulfonyldiphthalic anhydride (SDPA) had a better solubility than the other polyimides. These polyimides had glass transition temperatures between 248–286°C (DSC). Thermogravimetric analyses established that these polymers were fairly stable up to 500°C, and the 10% weight loss temperatures were recorded in the range of 549–595°C in nitrogen and 539–590°C in air atmosphere. © 1995 John Wiley & Sons, Inc.     

Synthesis and properties of polyimides derived from 1,7-bis(4-aminophenoxy)naphthalene and aromatic tetracarboxylic dianhydrides

The novel diamine, 1,7-bis(4-aminophenoxy)naphthalene (1,7-BAPON), was synthesized and used to prepared polyimides. 1,7-BAPON was synthesized through the nucleophilic displacement of 1,7-dihydroxynaphthalene with p-fluoronitrobenzene in the presence of K₂CO₃ followed by catalytic-reduction. Polyimides were prepared from 1,7-BAPON and various aromatic tetracarboxylic dianhydrides by the usual two-step procedure that included ring-opening polyaddition to give poly(amic acid)s, followed by cyclodehydration to polyimides. The poly(amic acid)s had inherent viscosities of 0.74-2.48 dL/g. Most of the polyimides formed tough, creasible films. These polyimides had glass transition temperatures between 247–278°C and their 10% weight loss temperatures were recorded in the range of 515–575°C in nitrogen atmosphere. © 1995 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 and polyimides derived from 3,3-bis [4-(4-aminophenoxy) phenyl] phthalide

3,3-Bis[4-(4-aminophenoxy)phenyl]phthalide ( II ) was used as a monomer with various aromatic dicarboxylic acids and dianhydrides to synthesize polyamides and polyimides, respectively. The diamine II was derived by a nucleophilic substitution of phenolphthalein with p-chloronitrobenzene in the presence of K₂CO₃. Polyamides IV _a-g having inherent viscosities of 0.77–2.46 dL/g were prepared by the direct polycondensation of diamine II with diacids III _a-g using triphenyl phosphite and pyridine as condensing agents. The polyamides were readily soluble in a variety of solvents such as N, N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), and N-methyl-2-pyrrolidinone (NMP) and afforded transparent and flexible films from the polymer solutions. These polymers had glass transition temperatures (T_gs) in the 227–307°C range and 10% weight loss temperatures occurred up to 450°C. Polyimides VI _a-e based on diamine II and various aromatic dianhydrides V _a-e were synthesized by the two-stage procedure that included ring-opening, followed by thermal or chemical conversion to polyimides. Most of the polyimides obtained by chemical cyclodehydration procedure were found to soluble in DMF, NMP, o-chlorophenol, and m-cresol. The T_gs of these polyimides were in the 260–328°C range and showed almost no weight loss up to 500°C under air and nitrogen atmosphere. © 1994 John Wiley & Sons, Inc.     

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.     

Synthesis and characterization of fluorine-containing polyamides derived from 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane by direct polycondensation

A fluorine-containing diamine, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (BAPPH) ( II ), was synthesized in two steps on condensation of 2,2-bis(4-hydroxyphenyl)hexafluoropropane with p-chloronitrobenzene in the presence of potassium carbonate, giving 2,2-bis[4-(4-nitrophenoxy)phenyl]hexafluoropropane ( I ), followed by reduction with hydrazine monohydrate/Pd—C. Fluorine-containing polyamides and copolyamides having inherent viscosities 0.41–0.88 dL g⁻¹ were prepared by direct polycondensation of BAPPH with various aromatic diacids or with mixed diacids, by triphenyl phosphite and pyridine in N-methyl-2-pyrrolidinone (NMP). The polyamides were examined by elemental analysis, IR spectra, inherent viscosity, x-ray diffraction, solubility, DSC, and TGA. The diffractogram showed that the polyamides were crystalline except IVb , IVc , IVf , and Vc . Almost all polyamides were soluble in polar aprotic solvents. The polymers obtained from BAPPH lost no mass below 350°C, with 10% loss of mass being recorded above 467°C in nitrogen. These aromatic polyamides had glass transition temperatures in the 221–253°C range. © 1996 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 polyimides derived from 1,4-bis(4-aminophenoxy)2,5-di-tert-butylbenzene

Novel aromatic polyimides containing symmetric, bulky di-tert-butyl substituents unit were synthesized from 1,4-bis(4-aminophenoxy)2,5-di-tert-butylbenzene (BADTB) and various aromatic tetracarboxylic dianhydrides by the conventional two-stage procedure that included ring-opening polyaddition in a polar solvent such as N,N-dimethylacetamide to give poly(amic acid)s, followed by cyclodehydration to polyimides. The diamine was prepared through the nucleophilic displacement of 2,5-di-tert-butylhydroquinone with p-chloronitrobenzene in the presence of K₂CO₃, followed by catalytic reduction. Depending on the dianhydrides used, the poly(amic acid)s obtained had inherent viscosities of 0.83–1.88 dL g⁻¹. Most of the polyimides formed transparent, flexible, and tough films. Tensile strength and elongation at break of the BADTB-based polyimide films ranged from 68–93 MPa and 7–11%, respectively. The polyimide derived from 4,4′-hexafluoro-isopropylidenebisphathalic anhydride had better solubility than the other polyimides. These polyimides had glass transition temperatures between 242–298°C and 10% mass loss temperatures were recorded in the range of 481–520°C in nitrogen. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1527–1534, 1997     

Synthesis and properties of novel aromatic poly(ester amide)s derived from 1,5-bis(4-aminobenzoyloxy)naphthalene and aromatic dicarboxylic acids

A new naphthalene ring-containing bis(ester amine), 1,5-bis(4-aminobenzoyloxy)naphthalene (2), was synthesized from the condensation of 1,5-dihydroxynaphthalene with 4-nitrobenzoyl chloride followed by catalytic hydrogenation. A series of naphthalene-containing poly(ester amide)s having inherent viscosities of 0.34-0.82 dl/g were prepared by the direct phosphorylation polyamidation from bis(ester amine) 2 with various aromatic dicarboxylic acids. The poly(ester amide)s derived from terephthalic acid, 4,4′-biphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 4,4′-oxydibenzoic acid were semicrystalline and showed less solubility. The other polymers were amorphous and readily soluble in polar organic solvents and gave flexible and tough films via solution casting. Except for four examples, the poly(ester amide)s displayed discernible glass transitions between 190 and 227 °C by differential scanning calorimetry. These poly(ester amide)s did not show significant decomposition below 400 °C in nitrogen or air.     

Synthesis and properties of aromatic polyamides containing the cyclohexane structure

1,1-Bis[4-(4-carboxyphenoxy)phenyl]cyclohexane (III) and 1,1-bis[4-(4-aminophenoxy)phenyl]cyclohexane (V) were prepared in two main steps starting from the aromatic nucleophilic substitution of p-fluorobenzonitrile and p-chloronitrobenzene, respectively, with 1,1-bis(4-hydroxyphenyl)cyclohexane in the presence of potassium carbonate in N,N-dimethylformamide (DMF). Using triphenyl phosphite and pyridine as condensing agents, two series of polyamides with cyclohexylidene cardo groups were directly polycondensated from dicarboxylic acid III with various aromatic diamines or from diamine V with various aromatic dicarboxylic acids in an N-methyl-2-pyrrolidone (NMP) solution containing dissolved calcium chloride. The polyamides exhibited inherent viscosities in the range of 0.45 to 1.78 dL/g. Almost all of the polymers were readily soluble in polar aprotic solvents such as NMP and N,N-dimethylacetamide (DMAc) and could afford transparent, flexible, and tough films by solution casting. The glass transition temperatures (T_g) of these aromatic polyamides were in the range of 180–243°C by DSC, and the 10% weight loss temperatures in nitrogen and air were all above 450°C. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3575–3583, 1999     

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     

Synthesis and properties of poly(ether imide)s derived from 2,7-bis(3,4-dicarboxyphenoxy)naphthalene dianhydride and various aromatic diamines

A naphthalene unit-containing bis(ether anhydride), 2,7-bis(3,4-dicarboxyphenoxy)naphthalene dianhydride, was prepared in three steps starting from the nucleophilic nitrodisplacement reaction of 2,7-dihydroxynaphthalene and 4-nitrophthalonitrile in N,N-dimethylformamide (DMF) solution in the presence of potassium carbonate followed by alkaline hydrolysis of the intermediate bis(ether dinitrile) and subsequent dehydration of the resulting bis(ether diacid). High-molar-mass aromatic poly(ether imide)s were synthesized using a conventional two-stage polymerization process from the bis(ether anhydride) and ten aromatic diamines. The intermediate poly(ether amic acid)s had inherent viscosities of 0.95–2.67 dL/g. The films of poly(ether imide)s derived from two rigid diamines, that is, p-phenylenediamine and benzidine, crystallized and embrittled during the thermal imidization process. The other poly(ether imide)s belonged to amorphous materials and could be fabricated into transparent, flexible, and tough films. These poly(ether imide) films had yield strengths of 91–115 MPa, tensile strengths of 89–136 MPa, elongation to break of 11–45%, and initial moduli of 1.7–2.2 GPa. The T_gs of poly(ether imide)s were recorded in the range of 222–256°C depending on the nature of the diamine moiety. All polymers were thermally stable up to 500°C, with 10% weight loss being recorded above 540°C in air and nitrogen atmospheres. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2281–2287, 1997     

Synthesis and properties of poly(ether imide)s derived from 2,6-bis(3,4-dicarboxyphenoxy)naphthalene dianhydride and aromatic diamines

A new naphthalene unit-containing bis(ether anhydride), 2,6-bis(3,4-dicarboxyphenoxy)naphthalene dianhydride, was synthesized in three steps starting from the nucleophilic nitrodisplacement reaction of 2,6-dihydroxynaphthalene and 4-nitrophthalonitrile in N,N-dimethylformamide (DMF) solution in the presence of potassium carbonate, followed by alkaline hydrolysis of the intermediate bis(ether dinitrile) and subsequent dehydration of the resulting bis(ether diacid). High-molar-mass aromatic poly(ether imide)s were prepared using a conventional two-step polymerization process from the bis(ether anhydride) and various aromatic diamines. The intermediate poly(ether amic acid)s had inherent viscosities of 0.65–2.03 dL/g. The films of poly(ether imide)s derived from two rigid diamines, i.e. p-phenylenediamine and benzidine, crystallized during the thermal imidization process. The other poly(ether imide)s belonged to amorphous materials and could be fabricated into transparent, flexible, and tough films. These aromatic poly(ether imide) films had yield strengths of 104–131 MPa, tensile strengths of 102–153 MPa, elongation to break of 8–87%, and initial moduli of 1.6–3.2 GPa. The glass transition temperatures (T_g's) of poly(ether imide)s were recorded in the range of 220–277°C depending on the nature of the diamine moiety. All polymers were stable up to 500°C, with 10% weight loss being recorded above 550°C in both air and nitrogen atmospheres. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1657–1665, 1998