Synthesis and properties of BCDA‐based polyimide–clay nanocomposites

Bicyclo[2.2.2]oct‐7‐ene‐2,3,5,6‐tetracarboxylic dianhydride (BCDA)‐based polyimide–clay nanocomposites were prepared from their precursor, namely polyamic acid, by a solution‐casting method. The organoclay was prepared by treating sodium montmorillonite (Kunipia F) clay with dodecyltrimethylammonium bromide at 80 °C. Polyamic acid solutions containing various weight percentages of organoclay were prepared from 4,4′‐(4,4′‐isopropylidenediphenyl‐1,1′‐diyldioxy)‐dianiline and BCDA in N‐methyl‐2‐pyrrolidone containing dispersed particles of organoclay at 20 °C. These solutions were cast on a glass plate using a Doctor's blade and then heated subsequently to obtain nanocomposite films. The nanocomposites were characterized using Fourier transform infrared spectroscopy, differential scanning calorimetry, thermal mechanical analysis, dynamic mechanical analysis, polarizing microscopy, scanning electron microscopy, transmission electron microscopy, wide‐angle X‐ray diffraction (WAXD) and thermogravimetric analysis. The glass transition temperature of the nanocomposites was found to be higher than that of pristine polymer. The coefficient of thermal expansion of the nanocomposites decreased with increasing organoclay content. WAXD studies indicated that the extent of silicate layer separation in the nanocomposite films depended upon the organoclay content. Tensile strength and modulus of the nanocomposite containing 1% organoclay were significantly higher when compared to pristine polymer and other nanocomposites. The thermal stability of the nanocomposites was found to be higher than that of pristine polymer in air and nitrogen atmosphere. Copyright © 2007 Society of Chemical Industry     

Synthesis and characterization of polyimide–silica nanocomposites using novel fluorine‐modified silica nanoparticles

Polyimide–silica nanocomposites were synthesized with 4,4′‐oxydianiline, 4,4′‐(4,4′‐isopropylidenediphenoxy)bis(phthalic anhydride), and fluorine‐modified silica nanoparticles. Fluorinated precursors such as 4″,4?‐(hexafluoroisopropylidene)bis(4‐phenoxyaniline) (6FBPA) and 4,4′‐(hexafluoroisopropylindene)diphenol (BISAF) were employed to modify the surface of the silica nanoparticles. The microstructures and thermal, mechanical, and dielectric properties of the polyimide–silica nanocomposites were investigated. An improvement in the thermal stability and storage modulus of the polyimide nanocomposites due to the addition of the modified silica nanoparticles was observed. The microstructures of the polyimide–silica nanocomposites containing 6FBPA‐modified silica exhibited more uniformity than those of the nanocomposites containing BISAF‐modified silica. The dielectric constants of the polyimide were considerably reduced by the incorporation of pristine silica or 6FBPA‐modified silica but not BISAF‐modified silica. The addition of a modifier with higher fluorine contents did not ensure a lower dielectric constant. The uniformity of the silica distribution, manipulated by the reactivity of the modifier, played an important role in the reduction of the dielectric constant. Using 6FBPA‐modified silica nanoparticles demonstrated an effective way of synthesizing low‐dielectric‐constant polyimide–silica nanocomposites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 882–890, 2007     

In situ preparation of transparent polyimide nanocomposite with a small load of graphene oxide

Polyimide (PI) nanocomposites with 4,4′‐bisphenol A dianhydride, 4,4′‐oxydiphthalic anhydride, and diaminodiphenyl methane (MDA) as comonomers and functionalized with graphene oxide (GO), were prepared by in situ polymerization. Only a small amount of GO (0.03–0.12 wt %) is added to improve the mechanical properties of PI and to avoid a substantial decrease of PI transparence. The nanocomposites are characterized by FTIR, X‐ray diffraction, thermogravimetric analysis, transmission electron microscope, tensile test, and UV‐vis spectroscopy. It is demonstrated that the PI/GO composite films possess transmittance of above 80% at wavelengths of 500–800 nm when the GO content is under 0.12 wt %, while the stress intensity and Young's modulus are improved by 29 and 25%, respectively. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and thermal,mechanical and gas permeation properties of aromatic polyimides containing different linkage groups

Two series of aromatic polyimides containing various linkage groups based on 2,7‐bis(4‐aminophenoxy)naphthalene or 3,3′‐dimethyl‐4,4′‐diaminodiphenylmethane and different aromatic dianhydrides, namely 4,4′‐(4,4′‐isopropylidenediphenoxy)bis(phthalic anhydride), 4,4′‐(hexafluoroisopropylidene)bis(phthalic anhydride), 3,3′,4,4′ benzophenonetetracarboxylic dianhydride, 9,9‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]fluorene dianhydride and 4,4′‐(4,4′‐hexafluoroisopropylidenediphenoxy)bis(phthalic anhydride), were synthesized and compared with regard to their thermal, mechanical and gas permeation properties. All these polymers showed high thermal stability with initial decomposition temperature in the range 475–525 °C and glass transition temperature between 208 and 286 °C. Also, the polymer films presented good mechanical characteristics with tensile strength in the range 60–91 MPa and storage modulus in the range 1700–2375 MPa. The macromolecular chain packing induced by dianhydride and diamine segments was investigated by examining gas permeation through the polymer films. The relationships between chain mobility and interchain distance and the obtained values for gas permeability are discussed. © 2014 Society of Chemical Industry     

New aramid‐based nanocomposites: Synthesis and characterization

New type of nanocomposites containing various proportions of montmorillonite in aromatic polyamide was prepared via solution intercalation method. Aramid chains were synthesized by reacting 4,4′‐oxydianiline with isophthaloyl chloride in N,N′‐dimethyl acetamide. Dodecylamine was used as swelling agent to change the hydrophilic nature of montmorillonite into organophilic. Appropriate amounts of organoclay were mixed in the polymer solution using high‐speed mixer for complete dispersion of the clay. Thin films cast from these materials after evaporating the solvent were characterized by XRD, TEM, mechanical, thermal, and water absorption measurements. The structure and morphology of the nanocomposites determined by XRD and TEM revealed the formation of exfoliated and intercalated clay platelets in the aramid matrix. Mechanical data indicated improvement in the tensile strength and modulus of the nanocomposites with clay loading up to 6 wt%. The glass transition temperature increased up to 12 wt% clay content and thermal stability amplified with increasing clay loading. The water absorption reduced gradually as a function of organoclay and approached to zero with 20 wt% organoclay in the aramid. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Development and characterization of co‐polyimide/attapulgite nanocomposites with highly enhanced thermal and mechanical properties

A series of co‐polyimide/attapulgite (co‐PI/AT) nanocomposites have been successfully fabricated from anhydride‐terminated polyimide (PI) and γ‐aminopropyltriethoxysilane (APTES)‐modified fibrous attapulgite (AT). Co‐PI was prepared from 4,4′‐diaminodiphenyl ether (ODA), 4,4′‐oxydiphthalic anhydride (ODPA), and 2,2‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]propane dianhydride (BPADA) by using the method of chemical imidization. Different amount of AT (0, 1, 3, 5, 7 wt%) were introduced into co‐PI via strong covalent interactions between terminal anhydride and amino groups. The properties of co‐PI/AT nanocomposites such as morphology, thermal stability, mechanical properties, and UV transparency were investigated to illustrate the contribution of the introduction of AT into the PI matrix. FTIR spectra and SEM images revealed that network structures between co‐PI and AT are formed, which endowed the nanocomposites with outstanding thermal and mechanical properties. The co‐PI/AT nanocomposites exhibited excellent thermal and thermo‐oxidative stabilities with the onset decomposition temperature and 10% weight loss temperature increasing to the ranges of 502–510°C and 555–562°C from 480°C to 526°C for the pristine co‐PI, respectively. The glass transition temperatures of these co‐PI/AT nanocomposites increased to the range of 231–238°C from 222°C for pure co‐PI. The co‐PI/AT nanocomposites films were found to be transparent, flexible, and tough. By incorporating 5 wt% AT into the co‐PI matrix, the tensile strength, elongation at break, and Young's modulus of the co‐PI/AT nanocomposites reached 110.7 MPa, 14.5%, and 1.2 GPa, respectively, which are 50%, 120%, and 80% increased compared with the values of pristine PI. POLYM. COMPOS., 35:86–96, 2014. © 2013 Society of Plastics Engineers     

Thermal and surface characterization of polyurethane–urea clay nanocomposite coatings

This paper reports synthesis and characterization of polyurethane–urea (PU‐urea) and the nanocomposites derived from the PU‐urea with silicate clays. Organophilic montmorillonite cotreated by cetyl trimethyl ammonium bromide (CTAB) was synthesized and used to prepare PU‐urea/montmorillonite nanocomposites coatings. PU‐ureas were prepared from polyethylene glycol (PEG), polypropylene glycol (PPG), trimethylol propane (TMP), and 4,4′‐diphenylmethane diisocyanate (MDI) by reacting excess diisocyanate with polyether glycols. The excess isocyanate of the prepolymers was cured with atmospheric moisture. The synthesized moisture cured PU‐urea and nanocomposites were characterized by Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetric (DSC), and angle resolved X‐ray photoelectron spectroscopy (AR‐XPS). The thermal stability of the PU‐urea nanocomposites was higher relative to the mother PU‐urea films. DSC results showed a slight enhancement in the soft segment glass transition temperature after 3 wt % clay loading. The surface properties showed an enrichment of the soft segment toward the surface. An enhancement in the hard segment composition in the nanocomposite coatings has resulted in enhancing the phase mixing process. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2393–2401, 2006     

Poly(amide‐imide)/organoclay nanocomposites using glycine as a natural amino acid: study on fire and thermal behavior

In the present study, new functional poly(amide‐imide)/organoclay nanocomposite films were successfully fabricated through the solution intercalation technique. New poly(amide‐imide) (PAI) containing glycine was synthesized via solution polycondensation of 1,1',3,3'‐tetraoxo(5,5'‐biisoindoline‐2,2'‐diyl)diacetic acid with 4,4′‐diaminodiphenylsulfone. The synthesized PAI was characterized by ¹H NMR, Fourier transform infrared (FTIR) spectroscopy, gel permeation chromatography, elemental analysis and inherent viscosity. Then, PAI/organoclay nanocomposite films containing 4 and 8 wt% of organoclay were prepared via solution intercalation through blending of organoclay 30B with the PAI solution. The nanostructures and properties of the PAI/organoclay were investigated using FTIR spectroscopy, XRD, transmission electron microscopy (TEM), TGA, DSC and microscale combustion calorimetry. XRD and TEM revealed the good dispersion of organoclay in the polymer matrix. TGA indicated that the addition of organoclay into the PAI matrix increases the thermal decomposition temperatures and char yields of the nanocomposites. Organoclay shows a positive effect in improving the flame retardancy of the PAI, reflecting the decrease in heat release rate, the total heat release and the heat release capacity of the PAI nanocomposites, while the thermal stability of the PAI nanocomposites only increased slightly compared with the neat polymer. © 2013 Society of Chemical Industry     

Synthesis of highly soluble and transparent polyimides

A novel aromatic diamine, 3,3′‐diisopropyl‐4,4′‐diaminophenyl‐4″‐methyltoluene with a 4‐methylphenyl pendant group and isopropyl side groups, was designed and synthesized in this study. Then it was polymerized with various aromatic dianhydrides including pyromellitic dianhydride, 3,3′,4,4′‐biphenyltetracarboxylic dianhydride, 4,4′‐oxydiphthalic anhydride, 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride and 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride via a one‐pot high temperature polycondensation procedure to produce a series of aromatic polyimides. These polyimides exhibited excellent solubility even in common organic solvents, such as chloroform and tetrahydrofuran. The flexible and tough films can be conveniently obtained by solution casting. The films were nearly colorless and exhibited high optical transparency, with the UV cutoff wavelength in the range 302–365 nm and the wavelength of 80% transparency in the range 385–461 nm. Moreover, they showed low dielectric constants (2.73–3.23 at 1 MHz) and low moisture absorption (0.13%–0.46%). Furthermore, they also possessed good thermal and thermo‐oxidative stability with 10% weight loss temperatures (T_10%) in the range 489–507 °C in a nitrogen atmosphere. The glass transition temperatures of all polyimides are in the range 262–308 °C. Copyright © 2012 Society of Chemical Industry     

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     

4,4′‐Bismaleimidodiphenyl methane modified novolak resin/titania nanocomposites: Preparation and properties

4,4′‐Bismaleimidodiphenyl methane modified novolak resin/titania nanocomposites were prepared by the sol–gel process of tetrabutyl titanate in the presence of 4,4′‐bismaleimidodiphenyl methane modified novolak resin prepolymers with acetyl acetone as a stabilizer. These nanocomposite materials were characterized by Fourier transform infrared analysis, dynamical mechanical analysis, thermogravimetric analysis, transmission electron microscopy, and field emission scanning electron microscopy. Nanometer titania particles were formed in the novolak resin matrix, and the average original particle size of the dispersed phase in the nanocomposites was less than 150 nm, but particle aggregates of larger size existed. The introduction of the titania inorganic phase with a nanoscale domain size did not improve the glass‐transition temperature of the nanocomposites but lowered the thermal resistance of the material because of the incomplete removal of acetyl acetone coordinated with tetrabutyl titanate, and it improved the modulus of the material at lower temperatures (<200°C) but lowered the modulus at higher temperatures (>250°C). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 52–57, 2006     

Synthesis and characterization of soluble poly(ether imide)s containing fluorenyl cardo groups

Two series of poly(ether imide)s (PEIs) containing fluorenyl cardo groups in the main chains were synthesized, which are derived from the polycondensation of 9,9′‐bis(4‐aminophenoxyphenyl)fluorene (BAOFL) or 9,9′‐bis(3‐trifluoromethyl,4‐aminophenoxyphenyl)fluorene (6F‐BAOFL) with four kinds of dianhydrides (3,3′,4,4′‐biphenyltetracarboxylic dianhydride, 4,4′‐oxydiphthalicanhydride, 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride, and bisphenol‐A dianhydride), respectively. The PEI films and PEI powder were prepared by thermal and chemical imidization, respectively. The PEIs were characterized by FTIR, ¹H‐NMR, differential scanning calorimetry, thermogravimetric analysis, and UV–vis were performed on inherent viscosity, solubility, and tensile tests. The effects of fluorenyl cardo groups and ether linkages on the solubility, tensile properties, thermal stability, and optical properties were investigated in detail. It was found that the PEIs had good solubility in common organic solvents and good optical transparency in visible light region. In addition, the PEI films exhibited excellent tensile and thermal properties. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and properties of elastic polyurethane‐imide

A new synthesis route for elastic polyurethane‐imides (EPUIs) has been established by a method involving the use of urea. Various EPUIs were synthesized from polyurethane‐urea, which was prepared from 4,4′‐diphenylmethane diisocyanate (MDI), polyoxytetramethylene glycol (PTMG) and 4,4′‐diphenylmethanediamine (MDA), and pyromellitic dianhydride in N‐methyl‐2‐pyrrolidone (NMP). Flexible films were cast from these solutions that had different inherent viscosities. Imidization of the EPUI films was completed at 200°C for 4 h in vacuo. The EPUIs were determined by FTIR, ¹H NMR, and ¹³C NMR spectra. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and properties of the amino‐functionalized multiple‐walled carbon nanotubes/polyimide nanocomposites

The 1,6‐hexanediamine‐functionalized multi‐walled carbon nanotubes(a‐MWNTs)/polyimide(PI) nanocomposite films were prepared through in‐situ polymerization followed by mixture casting, evaporation, and thermal imidization. To increase the compatibility of carbon nanotubes with the matrix polyimide, a‐MWNTs was used as the filler. According to the results, a‐MWNTs were homogeneously dispersed in the nanocomposite films. With the incorporation of a‐MWNTs, the mechanical properties of the resultant films were improved due to the strong chemical bonding and interfacial interaction between a‐MWNTs and 4,4′‐oxydiphthalic anhydride(ODPA)/4,4′‐Oxydianiline(ODA) polyimide matrix. The thermal stability of the a‐MWNTs/polyimide nanocomposite was also improved by the addition of a‐MWNTs. The electrical tests showed a percolation threshold at about 0.85 vol% and the electrical properties were increased sharply. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Nanocomposites of a bismaleimide resin with octaphenylsilsesquioxane or nano‐SiO2

Nanocomposites were prepared from the resin of 4,4′‐bismaleimido‐diphenylmethane (BDM) with dipropargyl ethers of hexafluorobisphenol A (DPBPF) and octaphenylsilsesquioxane (OPS) or nano‐SiO₂. The nanocomposites were characterized by Fourier transform infrared spectroscopy, scanning electron microscope, dynamic mechanical analysis and thermogravimetric analysis. The results exhibited that OPS or nano‐SiO₂ particles could be easily dispersed in the nanocomposites and the glass transition and decomposition temperatures of c‐BDM‐DPBPF‐OPS and c‐BDM‐DPBPF‐SiO₂ nanocomposites were higher than those of c‐BDM‐DPBPF resin. The reinforcement of OPS was more effective than that of nano‐SiO₂ in the nanocomposites. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers     

Development of Functional Polyurethane–ZnO Hybrid Nanocomposite Coatings from Thevetia peruviana Seed Oil

The present article reports eco‐friendly multi‐functional polyurethane–ZnO hybrid nanocomposite coatings obtained from Thevetia peruviana seed oil (TPSO). Initially, the polyols were prepared by treating TPSO with glycerol and the formation was supported by Fourier transform infrared (FT‐IR) and ¹H‐NMR studies. In the next stage, siloxane functionalized ZnO nanoparticles were added to the polyol mixture in different weight percentages (0, 1 and 2 %) and then treated with excess 4,4′‐diisocyanatodicyclohexylmethane (H₁₂MDI) in order to synthesize isocyanate terminated polyurethane nanocomposites. The polyurethane hybrids were then casted as thin films and cured under atmospheric moisture. After complete curing they were characterized by using FT‐IR, ¹H‐NMR, ¹³C‐NMR, X‐ray diffraction, scanning electron microscopy, thermogravimetric analysis, and dynamic mechanical thermal analysis techniques. The hybrid nanocomposites showed superior thermo‐mechanical and anti‐corrosive properties compared to pristine polyurethane. Also, due to the presence of nano ZnO in the polyurethane matrix, the composite coatings are showing excellent resistance towards various bacterial and fungal stains.     

Synthesis and thermal properties of organically modified palygorskite/fluorinated polyurethane nanocomposites

In this article, fluorinated polyurethane (FPU) nanocomposites filled with organic modified palygorskite (Pal) were synthesized and characterized by Fourier transform infrared, X‐ray diffraction, thermogravimetric analysis (TGA), and scanning electron microscope individually. The Pal nanorods were modified with 4,4′‐methylene (MDI) by chemical bond. TGA results showed that there are almost 27 wt % of 4,4′‐methylene grafting or absorbing on Pal nanorods’ surface. Compared with neat FPU, FPU nanocomposites exhibited somewhat increase in the soft segment glass transition temperature and decrease in the hard segment glass transition temperature. It means the compatibility between soft segment and hard segment becomes better than neat FPU. TGA results also showed that the thermal stability of FPU nanocomposites improved with increasing modified Pal loadings. Pal showed good compatibility with the FPU matrix through scanning electron microscope test results. And, the introduction of Pal into FPU matrix will not affect migration of fluoride side chain. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45460.     

Synthesis and properties of ultralow dielectric constant porous polyimide films containing trifluoromethyl groups

In this research, a series of porous copolyimide (co‐PI) films containing trifluoromethyl group (CF₃) were facilely prepared via a phase separation process. The co‐PI were synthesized by the reaction of benzophenone‐3,3′,4,4′‐tetracarboxylic dianhydride (BTDA) with two diamines of 4,4′‐diaminodiphenyl ether (ODA) and 3‐trifluoromethyl‐4,4'‐diaminodiphenyl ether (FODA) with various molar ratios. The flexible and tough porous co‐PI films with about 300 μm thickness and 8～10 μm average diameter could be obtained by solution casting conveniently. The thermal properties of the obtained porous co‐PI films were excellent with a glass transition temperature at 270 °C ～ 280 °C and only 5% weight loss in temperature from 530 °C to 560 °C under nitrogen atmosphere. In addition, the dielectric and hydrophobic properties of porous co‐PI films were remarkably improved owing to the presence of trifluoromethyl groups (CF₃) in the polymer chains. Moreover, our synthesized porous co‐PI films also showed good mechanical properties. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44494.     

Film studies of certain new aromatic–aliphatic polyamides

Two new aromatic–aliphatic polyamides containing azo linkage in the main chain based on 2,2′‐dimethyl‐4,4′‐diaminoazobenzene and adipic/2‐chloro‐5‐methyl‐1,2‐dioic acid (α‐chloro‐δ‐methyl adipic acid) were synthesized and analyzed by thermogravimetry and films were cast. Also three polymers obtained from condensation of 4,4′‐azodibenzoic acid/adipic acid and 2,2′‐bis [4‐(p‐amino phenoxy) phenyl] propane/4,4′‐diaminoazobenzene were studied in terms of mechanical and morphological properties. Film studies were carried out interms of tensile property, scanning electron microscope, dielectric, microwave, and X‐ray diffraction pattern. Thermal studies have been done using thermogravimetric analysis, differential thermal analysis, and pyrolysis‐mass spectral data. The results were correlated with structure and orientation of the molecules. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1305–1316, 2004     

Residual stress and mechanical properties of polyimide thin films

Four different structure polyimide thin films based on 1,4‐phenylene diamine (PDA) and 4,4′‐oxydianiline (ODA) were synthesized by using two different dianhydrides, pyromellitic dianhydride (PMDA) and 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA), and their residual stress behavior and mechanical properties were investigated by using a thin film stress analyzer and nanoindentation method. The residual stress behavior and mechanical properties were correlated to the morphological structure in polyimide films. The morphological structure of polyimide thin films was characterized by X‐ray diffraction patterns and refractive indices. The residual stress was in the range of ?5 to 38 MPa and increased in the following order: PMDA‐PDA < BPDA‐PDA < PMDA‐ODA < BPDA‐ODA. The hardness of the polyimide films increased in the following order: PMDA‐ODA < BPDA‐ODA < PMDA‐PDA < BPDA‐PDA. The PDA‐based polyimide films showed relatively lower residual stress and higher hardness than the corresponding ODA‐based polyimide films. The in‐plane orientation and molecularly ordered phase were enhanced with the increasing order as follows: PMDA‐ODA < BPDA‐ODA < BPDA‐PDA ～ PMDA‐PDA. The PDA‐based polyimides, having a rigid structure, showed relatively better‐developed morphological structure than the corresponding ODA‐based polyimides. The residual stress behavior and mechanical properties were correlated to the morphological structure in polyimide films. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009