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 characterization of new fluorene‐based poly(ether imide)s

A novel bis(ether anhydride) monomer, 9,9‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]fluorene dianhydride (4), was synthesized from the nitrodisplacement of 4‐nitrophthalonitrile by the bisphenoxide ion of 9,9‐bis(4‐hydroxyphenyl)fluorene (1), followed by alkaline hydrolysis of the intermediate tetranitrile and dehydration of the resulting tetracarboxylic acid. A series of poly(ether imide)s bearing the fluorenylidene group were prepared from the bis(ether anhydride) 4 with various aromatic diamines 5a–i via a conventional two‐stage process that included ring‐opening polyaddition to form the poly(amic acid)s 6a–i followed by thermal cyclodehydration to the polyimides 7a–i. The intermediate poly(amic acid)s had inherent viscosities in the range of 0.39–1.57 dL/g and afforded flexible and tough films by solution‐casting. Except for those derived from p‐phenylenediamine, m‐phenylenediamine, and benzidine, all other poly(amic acid) films could be thermally transformed into flexible and tough polyimide films. The glass transition temperatures (T_g) of these poly(ether imide)s were recorded between 238–306°C with the help of differential scanning calorimetry (DSC), and the softening temperatures (T_s) determined by thermomechanical analysis (TMA) stayed in the range of 231–301°C. Decomposition temperatures for 10% weight loss all occurred above 540°C in an air or a nitrogen atmosphere. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1403–1412, 1999     

Synthesis and characterization of new type soluble poly(amide–imide)s based on 6FDA imide modified polyterephthalamides

A series of new poly(amide–imide)s (PAIs, series III ) with good processability and characteristics was synthesized by utilizing organosoluble polyimide (PI, 6FDA–PI series) to improve poor‐solubility polyamide (PA, PTPA series), which used terephthalic acid (TPA) as a monomer. The III series PAIs were synthesized starting from the 2 : 1 molar ratio of aromatic diamines ( I ) and 6FDA to prepare imide ring‐preformed diamines ( II ) and then reacted with equimolar amount of TPA by direct polycondensation. Furthermore, by adjustment of the stoichiometry of the I , II, and TPA monomers, PAIs IV having various components were prepared. Most of the resulting PAIs having inherent viscosities between 0.70 and 1.74 dL/g were obtained in quantitative yields, and they were readily soluble in polar solvents such as N,N‐dimethylacetamide, N‐methyl‐2‐pyrrolidone, dimethylformamide, and dimethyl sulfoxide. All of the soluble PAIs afforded transparent, flexible, and tough films. The glass‐transition temperatures of PAIs III were in the range of 236–256 °C, and the 10% weight loss temperatures were recorded at 522–553 °C in nitrogen. The char yields of the III series polymers in nitrogen atmosphere were all higher than 56% even at 800 °C. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 93–104, 2001     

New light‐colored poly(ether imide)s based on 2,5‐di‐tert‐butylhydroquinone bis(ether anhydride) and aromatic diamines

A series of poly(ether imide)s (PEIs), III _a–k , with light color and good physical properties were prepared from 1,4‐bis(3,4‐dicarboxypheoxy)‐2,5‐di‐tert‐butylbenzene dianhydride ( I ) with various aromatic diamines ( II _a–k ) via a conventional two‐stage procedure that included a ring‐opening polyaddition to yield poly(amic acid)s (PAA), followed by thermal imidization to the PEI. The intermediate PAA had inherent viscosities in the range of 1.00–1.53 dL g^?1. Most of the PEIs showed excellent solubility in chlorinated solvents such as dichloromethane, chloroform, and m‐cresol, but did not easily dissolve in dimethyl sulfoxide and amide‐type polar solvents. The III series had tensile strengths of 96–116 MPa, an elongation at break of 7–8%, and initial moduli of 2.0–2.5 GPa. The glass‐transition temperatures (T_g) and softening temperatures (T_s's) of the III series were recorded between 232 and 285 °C and 216–279 °C, respectively. The decomposition temperatures for 10% weight loss all occurred above 511 °C in nitrogen and 487 °C in air. The III series showed low dielectric constants (2.71–3.54 at 1 MHz), low moisture absorption (0.18–0.66 wt %), and was light‐colored with a cutoff wavelength below 380 nm and a low yellow index (b^*) values of 7.3–14.8. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1270–1284, 2005     

Synthesis and characterization of poly(aryl amide imide)s derived from diphenyltrimellitic anhydride

The synthesis and characterization of a series of novel poly(aryl amide imide)s based on diphenyltrimellitic anhydride are described. The poly(aryl amide imide)s, having inherent viscosities of 0.39–1.43 dL/g in N-methyl-2-pyrrolidinone at 30°C, were prepared by polymerization with aromatic diamines in N,N-dimethylacetamide and subsequent chemical imidization. All the polymers were amorphous, readily soluble in aprotic polar solvents such as DMAC, NMP, dimethylsulfoxide, N,N-dimethylformamide, and m-cresol, and could be cast to form flexible and tough films. The glass transition temperatures were in the range of 284–366°C, and the temperatures for 5% weight loss in nitrogen were above 468°C. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4541–4545, 1999     

Synthesis and properties of new adamantane‐based poly(ether imide)s

A new adamantane‐based bis(ether anhydride), 2,2‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]adamantane dianhydride, was prepared in three steps starting from nitrodisplacement of 4‐nitrophthalonitrile with the potassium phenolate of 2,2‐bis(4‐hydroxyphenyl)adamantane. A series of adamantane‐containing poly(ether imide)s were prepared from the adamantane‐based bis(ether anhydride) and aromatic diamines by a conventional two‐stage synthesis in which the poly(ether amic acid)s obtained in the first stage were heated stage‐by‐stage at 150–270°C to give the poly(ether imide)s. The intermediate poly(ether amic acid)s had inherent viscosities between 0.56 and 1.92 dL/g. Except for those from p‐phenylenediamine, m‐phenylenediamine, and benzidine, all the poly(ether amic acid) films could be thermally converted into transparent, flexible, and tough poly(ether imide) films. All the poly(ether imide)s showed limited solubility in organic solvents, although they were amorphous in nature as evidenced by X‐ray diffractograms. Glass transition temperatures of these poly(ether imide)s were recorded in the range of 242–317°C by differential scanning calorimetry and of 270–322°C by dynamic mechanical analysis. They exhibited high resistance to thermal degrdation, with 10% weight loss temperatures being recorded between 514–538°C in nitrogen and 511–527°C in air. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1619–1628, 1999     

New poly(amide–imide)s syntheses. XXIII. Synthesis and properties of poly(amide–imide)s derived from 4,4′‐[1,4‐phenylenebis(isopropylidene‐1,4‐phenyleneoxy)]dianiline and various bis(trimellitimide)s

A series of poly(amide–imide)s III_a–m containing flexible isopropylidene and ether groups in the backbone were synthesized by the direct polycondensation of 4,4′‐[1,4‐phenylenebis(isopropylidene‐1,4‐phenyleneoxy)]dianiline (PIDA) with various bis(trimellitimide)s II_a–m in N‐methyl‐2‐pyrrolidone (NMP) using triphenyl phosphite and pyridine as condensing agents. The resulting poly(amide–imide)s had inherent viscosities in the range of 0.80–1.36 dL/g. Except for those from the bis(trimellitimide)s of p‐phenylenediamine and benzidine, all the polymers could be cast from DMAc into transparent and tough films. They exhibited excellent solubility in polar solvents. The 10% weight loss temperatures of the polymers in air and in nitrogen were all above 495°C, and their T_g values were in the range of 201–252°C. Some properties of poly(amide–imide)s III were compared with those of the corresponding poly(amide–imide)s V prepared from the bis(trimellitimide) of diamine PIDA and various aromatic diamines. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 69–76, 1999     

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 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     

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     

Synthesis and properties of soluble and light‐colored poly(amide‐imide‐imide)s on the basis of tetraimide‐dicarboxylic acid condensed from 4,4′‐oxydiphthalic anhydride, 2,2‐bis[4‐(4‐aminophenoxy)phenyl]propane,and m‐aminobenzoic acid,and various aromatic diamines

A new type of tetraimide‐dicarboxylic acid ( I ) was synthesized starting from the ring‐opening addition of m‐aminobenzoic acid, 4,4′‐oxydiphthalic anhydride, and 2,2‐bis[4‐(4‐aminophenoxy)phenyl]propane at a 2:2:1 molar ratio in N‐methyl‐2‐pyrrolidone (NMP), followed by cyclodehydration to the diacid I . A series of soluble and light‐colored poly(amide‐imide‐imide)s ( III _a–j) was prepared by triphenyl phosphite‐activated polycondensation from I with various aromatic diamines ( II _a–j). All films cast from N,N‐dimethylacetamide (DMAc) had cutoff wavelengths shorter than 390 nm (374–390 nm) and b* values between 25.26 and 43.61; these polymers were much lighter in color than the alternating trimellitimide series. All of the polymers were readily soluble in a variety of organic solvents such as NMP, DMAc, N,N‐dimethylformamide, dimethyl sulfoxide, and even in less polar m‐cresol and pyridine. Polymers III _a–j afforded tough, transparent, and flexible films that had tensile strengths ranging from 96 to 118 MPa, elongations at break from 9 to 11%, and initial moduli from 2.0 to 2.5 GPa. The glass‐transition temperatures of the polymers were recorded at 240–268 °C. They had 10% weight loss at a temperature above 540 °C and left more than 55% residue even at 800 °C in nitrogen. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 707–718, 2002; DOI 10.1002/pola.10153     

Synthesis and properties of aromatic polyamides based on 4,4′-(2,7-naphthalenedioxy)dibenzoic acid

4,4′-(2,7-Naphthalenedioxy)dibenzoic acid, a new aromatic dicarboxylic acid monomer, was prepared starting from 2,7-dihydroxynaphthalene and p-fluorobenzonitrile in three steps. Using triphenyl phosphite (TPP) and pyridine as condensing agents, a series of novel aromatic polyamides were synthesized by the direct polycondensation of the diacid monomer and aromatic diamines in N-methyl-2-pyrrolidone (NMP) solution containing dissolved calcium chloride. The resulting polyamides had inherent viscosities ranging from 0.48 to 0.67 dL/g. Most of these polyamides were readily soluble in polar solvents, such as NMP and N,N-dimethylacetamide (DMAc). Transparent, flexible, and tough films were cast from their DMAc solutions. They had tensile strengths of 65–70 MPa, elongations to break of 5–7%, and initial moduli of 1.4–1.6 GPa. Most of these polymers proved to be amorphous, with glass transition temperatures in the range between 143–227°C. Thermogravimetric analysis (TG) showed that all the polyamides were stable up to 450°C in both air and nitrogen atmospheres. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1469–1478, 1997     

Synthesis and properties of organosoluble polynaphthalimides based on 1,4,5,8‐naphthalene tetracarboxylic dianhydride, 3,3‐bis[4‐(4‐aminophenoxy)phenyl]phthalide,and various aromatic diamines

Two series of polynaphthalimides (PNIs), II and III , were prepared from 1,4,5,8‐naphthalene tetracarboxylic dianhydride with the usual aromatic diamines ( Ia – Ih ) or Ia , which was used as a soluble modifying agent, and Ib – Ih via a one‐stage process with high‐temperature condensation. Series II and III had inherent viscosities of 0.57–1.34 and 1.15–1.63 dL/g, respectively. IIa and most of the III series were soluble in 1‐methy‐2‐pyrrolidone and m‐cresol at 5–10 wt % and afforded transparent and tough films by m‐cresol solvent casting with a tensile strength in the range of 75–99 MPa. The glass‐transition temperature and softening temperature of these PNIs were in the ranges of 360–404 and 188–241 °C, respectively, and the 10% weight loss temperatures were above 495 °C, with more than a 44% char yield at 800 °C in nitrogen. These PNI films had dielectric constants of 4.14–6.46 (1 MHz), with moisture absorption in the range of 0.87–1.91 wt %. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 940–948, 2006     

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.     

Synthesis and characterization of new soluble polyamides derived from 3,3′,5,5′-tetramethyl-2,2-bis[4-(4-carboxyphenoxy)phenyl]propane

A series of new soluble polyamides having isopropylidene and methyl-substituted arylene ether moieties in the polymer chain were prepared by the direct polycondensation of 3,3′,5,5′-tetramethyl-2,2-bis[4-(4-carboxyphenoxy)phenyl]propane and various diamines in N-methyl-2-pyrrolidinone (NMP) containing CaCl₂ using triphenyl phosphite and pyridine as condensing agents. Polymers were produced with moderate to high inherent viscosities of 0.85–1.47 dL g⁻¹ while the weight-average molecular weight and number-average molecular weight were in the range of 86,700–259,000 and 43,300–119,000, respectively. All the polymers were readily dissolved in polar aprotic solvents such as NMP, N,N-dimethylacetamide, and N,N-dimethylformamide, as well as less polar solvents such as m-cresol and pyridine, and even soluble in tetrahydrofuran. These polymers were solution-cast into transparent, flexible and tough films. All of the polymers were amorphous and the polyamide films had a tensile strength range of 82–122 MPa, an elongation at break range of 6–18%, and a tensile modulus range of 2.0–2.8 GPa. These polyamides had glass transition temperatures between 233–260°C and 10% weight loss temperatures in the range of 450–489 and 459–493°C in nitrogen and air atmosphere, respectively. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1997–2003, 1999     

Synthesis of a new class of triphenylamine‐containing poly(ether‐imide)s for electrochromic applications

A novel triphenylamine (TPA)‐containing bis(ether anhydride) monomer, namely 4,4′‐bis(3,4‐dicarboxyphenoxy)triphenylamine dianhydride, was synthesized and reacted with various aromatic diamines leading to a series of new poly(ether‐imide)s (PEI). Most of these PEIs were soluble in organic solvents and could be easily solution cast into flexible and strong films. The polymer films exhibited good thermal stability with glass‐transition temperatures in the range 211–299 °C. The polymer films exhibited reversible electrochemical processes and stable color changes (from transparent to navy blue) with high coloration efficiency and contrast ratio upon electro‐oxidation. During the electrochemical oxidation process, a crosslinked polymer structure was developed due to the coupling reaction between the TPA radical cation moieties in the polymer chains. These polymers can be used to fabricate electrochromic devices with high coloration efficiency, high redox stability, and fast response time. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 825–838     

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     

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 cardo polyimides prepared from 5,5-Bis[4-(4-aminophenoxy)phenyl]-4,7-methanohexahydroindane

A new cardo diamine monomer, 5,5-bis[4-(4-aminophenoxy)phenyl]-4,7-methanohexahydroindane (II), was prepared in two steps with high yield. The monomer was reacted with six different aromatic tetracarboxylic dianhydrides in N,N-dimethylacetamide (DMAc) to obtain the corresponding cardo polyimides via the poly(amic acid) precursors and thermal or chemical imidization. All the poly(amic acid)s could be cast from their DMAc solutions and thermally converted into transparent, flexible, and tough polyimide films which were further characterized by x-ray and mechanical analysis. All of the polymers were amorphous and the polyimide films had a tensile strength range of 89–123 MPa, an elongation at break range of 6–10%, and a tensile modulus range of 1.9–2.5 GPa. Polymers V_c, V_e, and V_f exhibited good solubility in a variety of solvents such as N-methyl-2-pyrrolidinone (NMP), DMAc, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), pyridine, γ-butyrolactone, and even in tetrahydrofuran and chloroform. These polyimides showed glass-transition temperatures between 274 and 299°C and decomposition temperatures at 10% mass loss temperatures ranging from 490 to 521°C and 499 to 532°C in nitrogen and air atmospheres, respectively. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2815–2821, 1999     

Novel organosoluble and colorless poly(ether imide)s based on 3,3‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]phthalide dianhydride and aromatic bis(ether amine)s bearing pendent trifluoromethyl groups

A novel series of colorless and highly organosoluble poly(ether imide)s were prepared from 3,3‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]phthalide dianhydride with various fluorinated aromatic bis(ether amine)s via a conventional two‐stage process that included ring‐opening polyaddition to form the poly(amic acid)s followed by cyclodehydration to produce the polymer films. The poly(ether imide)s showed excellent solubility, with most of them dissoluble at a concentration of 10 wt % in amide polar solvents, in ether‐type solvents, and even in chlorinated solvents. Their films had a cutoff wavelength between 358 and 373 nm, and the yellowness index ranged from 3.1 to 9.5. The glass‐transition temperatures of the poly(ether imide) series were recorded between 237 and 297 °C, the decomposition temperatures at 10% weight loss were all above 494 °C, and the residue was more than 54% at 800 °C in nitrogen. These films showed high tensile strength and also were characterized by higher solubility, lighter color, and lower dielectric constants and moisture absorption than an analogous nonfluorinated polyimide series. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3140–3152, 2006