Bisphenol containing novel polyimides/glass fiber composites

A new diamine was synthesized using bisphenol‐A and p‐amino benzoic acid. Polyimides I and II were prepared with the diamine and pyromellitic dianhydride/3,3′,4,4′ benzophenone tetracarboxylic acid dianhydride. Bismaleimide (BMI) was synthesized using the same diamine and maleic anhydride. The prepared diamine and polyimides were characterized using FTIR. Thermo gravimetric analysis was used to study the thermal properties of synthesized polyimides and BMI. Woven glass fabric/unidirectional glass fiber‐polyimide/BMI composites were made and their properties (fiber volume fraction, density, tensile, flexural, impact, and hardness) were studied and compared with a few representative carbon fiber polyimide, carbon fiber–epoxy, and glass fiber–epoxy composites. The prepared composites were subjected to thermal aging and moisture absorption and their effects on tensile and flexural properties were studied. POLYM. COMPOS., 28: 372–380, 2007. © 2007 Society of Plastics Engineers     

Preparation and properties of organo‐soluble polyimides based on 4,4′‐diamino‐3,3‐dimethyldiphenylmethane and conventional dianhydrides

4,4′‐Diamino‐3,3′‐dimethyldiphenylmethane was used to prepare polyimides in an attempt to achieve good organo‐solubility and light color. Polyimides based on this diamine and three conventional aromatic dianhydrides were prepared by solution polycondensation followed by chemical imidization. They possess good solubility in aprotonic polar organic solvents such as N‐methyl 2‐pyrrolidone, N,N‐dimethyl acetamide, and m‐cresol. Polyimide from 4,4′‐diamino‐3,3′‐dimethyldiphenylmethane and diphenylether‐3,3′,4,4′‐tetracarboxylic acid dianhydride is even soluble in common solvents such as tetrahydrofuran and chloroform. Polyimides exhibit high transmittance at wavelengths above 400 nm. The glass transition temperature of polyimide from 4,4′‐diamino‐3,3′‐dimethyldiphenylmethane and pyromellitic dianhydride is 370°C, while that from 4,4′‐diamino‐3,3′‐dimethyldiphenylmethane and diphenylether‐3,3′,4,4′‐tetracarboxylic acid dianhydride is about 260°C. The initial thermal decomposition temperatures of these polyimides are 520–540°C. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1299–1304, 1999     

Functionalized KIT‐6/Terpolyimide composites with ultra‐low dielectric constant

Polyimides with low dielectric constants are important raw materials for the fabrication of flexible printed circuit boards and other microelectronic applications. As creation of voids in polyimide matrix could decrease dielectric constant, in this study mesoporous KIT‐6, synthesized hydrothermally, was functionalized with 3‐aminopropyltriethoxysilane (APTS) and mixed with 4,4′‐oxydianiline (ODA) in the synthesis of terpoly(amic acid) using 3,3′,4,4′‐biphenyldianhydride (BPDA), 3,3′,4,4′‐oxydiphthalic dianhydride (ODPA) and 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride (BTDA) and subsequently stage‐cured to obtain APTS‐KIT‐6/Terpolyimide composites (APTS‐KIT‐6/TPI). The asymmetric and symmetric vibrations of imide O?C? N? C?O groups of APTS‐KIT‐6/TPI composites showed their peaks at 1772 and 1713 cm^?1. The dielectric constant decreased with the increase in KIT‐6 loading from 2 to 4%, but increased at higher loadings, and at 4% loading it was 1.42. Its tensile strength (103 MPa), tensile modulus (2.5 GPa), and percentage elongation (8.2) and high thermal stability (>540°C) were also adequate for application in microelectronics such as flexible printed circuits. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40508.     

Preparation and characterization of quartz‐fiber‐cloth‐reinforced,polymerization‐of‐monomer‐reactant‐type polyimide substrates with a high impact strength

A series of novel quartz‐fiber‐cloth‐reinforced polyimide substrates with low dielectric constants were successfully prepared. For this purpose, the A‐stage polyimide solution was first synthesized via a polymerization‐of‐monomer‐reactant procedure with 2,2′‐bis(trifluoromethyl)benzidine and 3,3′,4,4′‐oxydiphthalic anhydride as the monomers, and cis?5‐norbornene‐endo‐2,3‐dicarboxylic anhydride as the endcap. Then, an A‐stage polyimide solution (TOPI) was impregnated with quartz‐fiber cloth (QF) to afford the prepregs, which were thermally molded into the final substrate composites. The influence of the curing temperature and the resin content on the mechanical properties of the composite were examined. The composites exhibited a high glass‐transition temperature over 360°C, a low and steady dielectric constant below 3.2 at a test frequency of 1–12 GHz, and a volume resistance over 1.8 × 10¹⁷ Ω cm. Meanwhile, they also showed a high mechanical strength with flexural and impact strengths in ranges 845–881 MPa and 141–155 KJ/m², respectively. The excellent mechanical and thermal properties and good dielectric properties indicated that they are good candidates for integrated circuit packaging substrates. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42358.     

Preparation and properties of glass cloth‐reinforced polyimide composites with improved impact toughness for microelectronics packaging substrates

A series of glass cloth‐reinforced thermosetting polyimide composites (EG/HTPI) were prepared from E‐glass cloth (EG) and polyimide matrix resins. The polyimide resins were derived from 1,4‐bis(4‐amino‐2‐ trifluoromethyl‐phenoxy)benzene, p‐phenylenediamine, diethyl ester of 3,3′,4,4′‐benzophenonetetracarboxylic acid, and monoethyl ester of cis‐5‐norbornene‐endo‐2,3‐dicarboxylic acid. Based on the rheological properties of the B‐staged polyimide resins, the optimized molding cycles were designed to fabricate the EG/HTPI laminates and the copper‐clad laminates (Cu/EG/HTPI). Experimental results indicated that the EG/HTPI composites exhibited high thermal stability and outstanding mechanical properties. They had flexural strength of >534 MPa, flexural modulus of >20.0 GPa, and impact toughness of >46.9 kJ/m². The EG/HTPI composites also showed good electrical and dielectric properties. Moreover, the EG/HTPI laminates exhibited peel strength of ～ 1.2 N/mm and great isothermal stability at 288°C for 60 min, showing good potential for application in high density packaging substrates. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Influence of chemical structure of polyimide prepolymer on rheo‐mechanical properties of polyimide foam composites

A study is reported of the effect of varying chemical composition of foam polyimide prepolymers (H‐complex) on the structure and properties of foam polyimide resins and their composites with aromatic polyimide fiber felt. The melt rheological behavior of the H‐complex was found to be strongly dependent on its chemical composition and structure reorganization in the melt which is akin to mesophasic structural transition states in liquid crystal polymers. Changing the diamine part of the H‐complex from 4,4‐methylene dianiline to 1,3‐diaminobenzene led to decreased steady shear viscosity at temperatures and shear rates ranging between 95° and 105°C and 0.01 and 1 s⁻¹, respectively. Additionally, changing the dialkyl moiety from dimethyl to diethyl in 3,3′,4,4′‐benzophenonetetracarboxylic dialkyl ester (precursor to the H‐complex) increased gelation time of the H‐complex, enhancing processibility of the foam polyimide composites. The results indicate that novel, lightweight foam polyimide composites with enhanced thermomechanical properties for beneficial uses can be prepared through chemical modification of the H‐complex prior to its thermal imidization in the presence of the aromatic polyimide fiber felt.     

Effect of monomer composition on properties of copolyimides derived from 3,3′,4,4′‐biphenyltetracarboxylic dianhydride/4,4′‐oxydianiline/1,3‐bis (4‐aminophenoxy)benzene

A series of uncontrolled molecular weight homopolyimides and copolyimides based on 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (s‐BPDA)/4,4′‐oxydianiline (4,4′‐ODA)/1,3‐bis(4‐aminophenoxy)benzene (TPER) were synthesized. All the polyimides displayed excellent thermal stability and mechanical properties, as evidenced by dynamic thermogravimetric analysis and tensile properties testing. A singular glass transition temperature (T_g) was found for each composite from either differential scanning calorimetry (DSC) or dynamic mechanical analysis (DMA), but the values determined from tan δ of DMA were much different from those determined from DSC and storage modulus (E′) of DMA. The Fox equation was used to estimate the random T_g values. Some composites exhibited re‐crystallization after quenching from the melt; upon heating, multi‐melting behavior was observed after isothermal crystallization at different temperatures. The equilibrium melting temperature was estimated using the Hoffman‐Weeks method. Additionally, DMA was conducted to obtain E′ and tan δ. Optical properties were strongly dependent on the monomer composition as evidenced by UV‐visible spectra. X‐ray diffraction was used to interpret the crystal structure. All the results indicated that composites with TPER composition ≥ 70% were dominated by the TPER/s‐BPDA polyimide phase, and ≤40% by the 4,4′‐ODA/s‐BPDA polyimide phase. When the ratio between the two diamines was close to 1:1, the properties of the copolyimides were very irregular, which means a complicated internal structure. Copyright © 2011 Society of Chemical Industry     

Fiber Reinforced Polyimide Aerogel Composites with High Mechanical Strength for High Temperature Insulation

Glass fiber/polyimide aerogel composites are prepared by adding glass fiber mat to a polyimide sol derived from diamine, 4,4′‐oxydianiline, p‐phenylene diamine, and dianhydride, 3,3′,4,4′‐biphenyltetracarboxylic dianhydride. The fiber felt acts as a skeleton for support and shaping, reduces aerogel shrinkage during the preparation process, and improves the mechanical strength and thermal stability of the composite materials. These composites possess a mesoporous structure with densities as low as 0.143–0.177 g cm^?3, with the glass fiber functioning to improve the overall mechanical properties of the polyimide aerogel, which results in its Young's modulus increasing from 42.7 to 113.5 MPa. These composites are found to retain their structure after heating at 500 °C, in contrast to pure aerogels which decompose into shrunken ball‐like structures. These composites maintain their thermal stability in air and N₂ atmospheres, exhibiting a low thermal conductivity range of 0.023 to 0.029 W m^?1 K^?1 at room temperature and 0.057to 0.082 W m^?1 K^?1 at 500 °C. The high mechanical strengths, excellent thermal stabilities, and low thermal conductivities of these aerogel composites should ensure that they are potentially useful materials for insulation applications at high temperature.     

Thermally stable polyimide binders from aromatic dianhydrides and acetyl derivatives of aromatic diamines: Formation mechanism

Polyimide resins based on dianhydrides of aromatic tetracarboxylic acids and acetyl derivatives of aromatic diamines have been developed for impregnating carbon fibers and glass cloth. Binder prepolymers are soluble in amide solvents and acetone and also form melts with a viscosity of 0.1–0.3 Pa · s at 250–300°C. The melt lifetime is 20–30 min. An increase in temperature leads to the formation of a crosslinked insoluble system of high thermal stability. The formation of polyimide binders was studied with the aid of IR and NMR spectroscopy. A mechanism of the reaction of aromatic dianhydrides with acylated amines is proposed. On the basis of polyimide binders from dianhydride of 3,3′,4,4′-benzophenonetetracarboxylic acid and bis-[4-acetaminophenyl]-sulfone, bis-[4-acetaminophenyl]-ether, and N,N-diacetyl-p-phenylene diamine, carbon fiber composites with good physico-mechanical properties were obtained.     

High temperature organic/inorganic addition cure polyimide composites,part 1: Matrix thermal properties

Structure‐thermal property interrelationships are characterized and reported for organic/inorganic addition cure polyimide composite matrices based on 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride, the reactive terminal group 4‐phenylethynyl phthalic anhydride, and stoichiometric controlled diamine ratios of 1,3‐phenylenediamine, 1,4‐phenylenediamine, or 4,4′‐(1,3‐phenylenediisopropylidene) bisaniline, combined with bis(p‐aminophenoxy) dimethyl silane or an α, ω‐bis(3‐aminopropyl) polydimethylsiloxane oligomer. Polymerization of monomer reactants resin solutions, carbon fiber prepregs and composites, and imidized oligomers are characterized to relate molecular chemical structure and morphology to glass transition temperature, processing characteristics, thermodynamic properties, and thermal stability. Glass transition temperature, thermal decomposition temperature, and char yield were found to increase with increasing siloxane block length in the imide backbone. As the concentration of inorganic component in the imide oligomer backbone increased, the cured glass transition temperature decreased. Char yield and thermal decomposition temperature were observed to decrease as the inorganic component concentration increased. Incorporation of bis(p‐aminophenoxy) dimethyl silane into the imide oligomer structure did not provide any significant advantages over traditional polyimides relative to thermal properties or composite processing, but aminosiloxanes improved composite toughness, prepreg tack, and composite processability. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and properties of polyimide/silica hybrid composites based on polymer‐modified colloidal silica

A new type of polyimide/silica (PI/SiO₂) hybrid composite films was prepared by blending polymer‐modified colloidal silica with the semiflexible polyimide. Polyimide was solution‐imidized at higher temperature than the glass transition temperature (T_g) using 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA) and 4,4′‐diaminodiphenyl ether (ODA). The morphological observation on the prepared hybrid films by scanning electron microscopy (SEM) pointed to the existence of miscible organic–inorganic phase, which resulted in improved mechanical properties compared with pure PI. The incorporation of the silica structures in the PI matrix also increased both T_g and thermal stability of the resulting films. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2053–2061, 2006     

Preparation and properties of soluble copolysulfoneimide and performance of solvent‐resistant ultrafiltration membrane

Soluble copolysulfoneimides were synthesized by thermal two‐step method in solution of N‐methyl‐2‐pyrrolidone. The used aromatic diamines were bis[4‐(3‐aminophenoxy)phenyl]sulfone (BAPS‐m) and 3,3′‐diaminosulfone, and dianhydrides were pyromellitic dianhydride, 4,4′‐oxyphthalic anhydride, and 3,3′,4,4′‐diphenylsulfone tetracarboxylic dianhydride. The molar ratio of diamines was changed to reduce the content of BAPS‐m. The thermal and mechanical properties of polyimides were investigated. The polyimide ultrafiltration membrane with molecular weight cut‐off of 10 kDa could be successfully prepared by phase‐inversion method. Various solvent (water, alcohols, acetone, and hexane) fluxes were measured to investigate solvent‐resistance and membrane behavior during solvent permeation. The activation energy relationship between hexane flux and viscosity with temperature was also studied. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1024–1030, 2002     

2,2′,6,6′-Tetrabromo-3,3′,5,5′-tetramethyl-4,4′-biphenol (TTB)–flame retardant copolycarbonates and copolyesters

2,2′,6,6′-Tetrabromo-3,3′,5,5′-tetramethyl-4,4′-biphenol (TTB) is a new flame retardant monomer possessing a high degree of chemical and thermal stability. This brominated biphenol can be directly incorporated as a comonomer in condensation polymerizations. An example is the preparation of copolycarbonates of TTB and 2,2-(4-hydroxyphenyl)propane (BPA) via the aqueous caustic phosgenation method. The reaction of TTB with either ethylene oxide or ethylene chlorohydrin affords 4,4′-bis(2-hydroxyethoxy)-2,2′,6,6′-tetrabromo-3,3′,5,5′-tetramethylbiphenyl (TTB-Diol). This diol is melt polymerized into a series of terephthalate copolymers with 1,4 butanediol. The above copolymers possess flame retardancy, thermal stability, and good mechanical properties. These high-bromine-content copolymers are blended with nonhalogen-containing polymers to afford blends with specific degrees of flame resistance.     

Comparative study of silicon‐containing polyimides from different oxydianilines

Silicon‐containing polyimides were synthesized by solution polycondensation of bis(3,4‐dicarboxyphenyl)dimethylsilane dianhydride with 3,4‐oxydianiline and 4,4′‐oxydianiline, respectively. All the poly(amic acid) films could be obtained by solution‐casting from N,N‐dimethylacetamide solutions and thermally converted into transparent and tough polyimide films. The physical properties of thin films of those polyimides were compared by DSC, TGA, UV–visible spectroscopy, and dynamic mechanical analysis. The polyimide from bis(3,4‐dicarboxyphenyl)dimethylsilane dianhydride and 3,4‐oxydianiline exhibited superior energy‐damping characteristic, mechanical properties, and optical transparency, whereas that from bis(3,4‐dicarboxyphenyl)dimethylsilane dianhydride and 4,4′‐oxydianiline possessed higher glass‐transition temperature and thermal stability. Because of the unsymmetric structure of the polyimide from bis(3,4‐dicarboxyphenyl)dimethylsilane dianhydride and 3,4‐oxydianiline, its increasing rate of linear coefficient of thermal expansion with temperature was quicker than that of the polyimide from bis(3,4‐dicarboxyphenyl)dimethylsilane dianhydride and 4,4′‐oxydianiline. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2363–2367, 2004     

Thermal properties of phosphorylated nanodiamond reinforced polyimides

Recently, the preparation of nanodiamond–polymer composites has attracted the attention of materials scientists due to the unique properties of nanodiamonds. In this study, novel polyimide (PI)/phosphorylated nanodiamonds (PNDs) composites were prepared. PNDs were achieved from the reaction of methylphosphonic dichloride with nanodiamonds in dichloromethane. Precursor of polyimide, which is the poly(amic acid) (PAA), was successfully synthesized with 3,3′, 4,4′‐benzophenonetetracarboxylic dianhydride and 4,4′‐oxydianiline in the solution of N,N‐dimethylformamide. Different ratios of phosphorylated nanodiamond particles were added into PAA solution and four different nanocomposite films were prepared. The amount of PNDs in the composite films was varied from 0 wt% to 3 wt%. The structure, thermal and surface properties of polyimide films were characterized by scanning electron microscopy (SEM), ATR‐FTIR, thermogravimetric analysis (TGA), ultraviolet visible spectroscopy, and contact angle. SEM and FTIR results showed that the phosphorylated nanodiamond and PI/PNDs films were successfully prepared. Phosphorylated nanodiamonds were homogeneously dispersed in the polymer matrix and they displayed good compatibility. TGA results showed that the thermo‐oxidative stability of PI/PNDs films was increased with the increasing amount of phosphorylated nanodiamond. POLYM. COMPOS., 37:2285–2292, 2016. © 2015 Society of Plastics Engineers     

Synthesis and characterization of novel polyimide/SiO2 nanocomposite materials containing phenylphosphine oxide via sol‐gel technique

In this article, a series of novel polyimide/silica (PI/SiO₂) nanocomposite coating materials were prepared from tetraethoxysilane (TEOS), γ‐glycidyloxypropyltrimethoxysilane (GOTMS), and polyamic acid (PAA) via sol‐gel technique. PAA was prepared by the reaction of 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride (BTDA) and bis (3‐aminophenyl) phenyphosphine oxide (BAPPO) in N‐methyl‐2‐ pyrrolidone (NMP). BAPPO was synthesized hydrogenation of bis (3‐nitrophenyl) phenyphosphine oxide (BNPPO) in the presence of Pd/C. The silica content in the hybrid coating materials was varied from 0 to 20 wt %. The molecular structures of the composite materials were analyzed by means of FT‐IR and ²⁹Si‐NMR spectroscopy techniques. The physical and mechanical properties of the nanocomposites were evaluated by various techniques such as, hardness, contact angle, and optical transmission and tensile tests. These measurements revealed that all the properties of the nanocomposite coatings were improved noticeable, by the addition of sol‐gel precursor into the coating formulation. Thermogravimetric analysis showed that the incorporation of sol‐gel precursor into the polyimide matrix leads to an enhancement in the thermal stability and also flame resistance properties of the coating material. The surface morphology of the hybrid coating was characterized by scanning electron microscopy (SEM). SEM studies indicated that nanometer‐scaled inorganic particles were homogenously dispersed throughout the polyimide matrix © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Novel phenylethynyl‐endcapped polyimide oligomers: Synthesis and characterization

A series of novel phenylethynyl‐endcapped polyimide oligomers were prepared by polycondensation of an aromatic diamine mixture of 1,3‐bis(4‐aminophenoxy) benzene (1,3,4‐APB) and 3,4′‐oxydianiline (3,4′‐ODA) with different aromatic dianhydrides including 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA), 4,4′‐(hexafluoro isopropylidene)diphthalic anhydride (6FDA), 4,4′‐oxydiphthalic anhydride (ODPA), and 4,4′‐[2,2,2‐trifluoro‐1‐(3′,5′‐bis‐(trifluoro‐methyl)phenyl)ethylidene]diphthalic anhydride (9FDA) in the presence of 4‐phenyl‐ethynylaniline (PEA) as endcapping agent in aprotic solvent at elevated temperature. The chemical structures, thermal behavior, and melt rheological properties of the synthesized polyimide oligomers were investigated. Experimental results indicated that the fluorinated polyimide oligomers derived from 6FDA (PI‐2) and 9FDA (PI‐4) are amorphous solid resins and exhibited lower melt viscosities than those prepared from the unfluorinated aromatic dianhydrides such as BPDA and ODPA. The BPDA‐based polyimide oligomers with a molar ratio of 1,3,4‐APB/3,4′‐ODA = 50:50 (PI‐5) showed lower melt viscosity than those derived from a mixture of 1,3,4‐APB and 3,4′‐ODA with molar ratios of 75:25 and 100:0, respectively. In addition, the melt viscosity of the polyimide oligomers increased obviously with increasing of the polymer calculated molecular weights. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Syntheses and properties of novel polyimides derived from 2‐(4‐Aminophenyl)‐5‐aminopyrimidine

2‐(4‐Aminophenyl)‐5‐aminopyrimidine (4) is synthesized via a condensation reaction of vinamidium salts and amidine chloride salts, followed by hydrazine palladium catalyzed reduction. A series of novel homo‐ and copolyimides containing pyrimidine unit are prepared from the diamine and 1,4‐phenylenediamine (PDA) with pyromellitic dianhydride (PMDA) or 3,3′,4,4′‐biphenyl tertracarboxylic dianhydride (BPDA) via a conventional two‐step thermal imidization method. The poly(amic acid) precursors had inherent viscosities of 0.97–4.38 dL/g (c = 0.5 g/dL, in DMAc, 30°C) and all of them could be cast and thermally converted into flexible and tough polyimide films. All of the polyimides showed excellent thermal stability and mechanical properties. The glass transition temperatures of the resulting polyimides are in the range of 307–434°C and the 10% weight loss temperature is in the range of 556–609°C under air. The polyimide films possess strength at break in the range of 185–271 MPa, elongations at break in the range of 6.8–51%, and tensile modulus in the range of 3.5–6.46 GPa. The polymer films are insoluble in common organic solvents, exhibiting high chemical resistance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5871–5876, 2006     

Preparation and properties of novel processable polyimides derived from N,N‐bis(isocyanatoalkyl)‐1,2,4,5‐benzenetetracarboxylic‐1,2:4,5‐diimides

Two diisocyanate monomers containing methylene groups and built‐in imide structure have been prepared from the parent diacids via the Curtius–Weinstock rearrangement. Polyimides have been synthesized by solution polymerization of these isocyanates with pyromellitic dianhydride (PMDA), 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride (BTDA), and hexafluoroisopropylidene‐2,2‐bis(phthalic‐anhydride) (6FDA). All monomers and polymers were characterized by conventional methods, and the physical properties of the polymers, including solution viscosity, solubility, thermal stability and thermal behaviour, were studied. © 2000 Society of Chemical Industry     

Synthesis of thermally stable aromatic poly(imide amide benzimidazole) copolymers

3,3′‐Dinitrobenzidine was first reacted with excess m‐chlorophenyl acid to form a monomer with dicarboxylic acid end groups. Two types of aromatic dianhydrides (Pyromellitic diconhydride (PMDA) and 3,3′,4,4′‐sulfonyl diphthalic anhydride) were also reacted with excess 4,4′‐diphenylmethane diisocyanate to form polyimide prepolymers terminated with isocyanate groups. The prepolymers were further extended with the diacid monomer to form nitro groups containing aromatic poly(imide amide). The nitro groups in these copolymers were hydrogenated to form amine groups and then were cyclized at 180°C to form poly(imide amide benzimidazole) in poly(phosphoric acid), which acted as a cyclization agent. The resultant copolymers were soluble in sulfuric acid and poly(phosphoric acid), in sulfolane under heating to 100°C, and in the polar solvent N‐methyl‐2‐pyrrolidone under heating to 100°C with 5% lithium chloride. According to wide‐angle X‐ray diffraction, all the copolymers were amorphous. According to thermal analysis, the glass‐transition temperatures of the copolymers were 270–322°C. The 10% weight‐loss temperatures were 460–541°C in nitrogen and 441–529°C in air. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1435–1444, 2003