Polyimides from isomeric biphenyltetracarboxylic dianhydrides and the effects of chemical structure on solubility

A series of homopolyimides and copolyimides was synthesized by the solution condensation of biphenyltetracarboxylic dianhydride (BPDA) isomers and various diamines followed by chemical imidization. These polyimides had intermediate to high molecular weights with inherent viscosities of 0.34–1.01 dL/g for homopolyimides and 0.48–1.02 dL/g for copolyimides. Thermogravimetric analysis indicated that the aromatic polyimides were stable up to 500°C, and the 5% weight loss temperatures were recorded in the range of 506–597°C in an air atmosphere and in the range of 517–601°C in a nitrogen atmosphere, depending on the diamines used. The glass transition temperatures of aromatic homopolyimides were above 271°C, while the glass transition temperatures of the copolyimides increased with an increase in the 2, 2′, 3, 3′‐BPDA‐component. The effects of the chemical structure of the polymer chain on the solubility were investigated. It was found that the solubility of BPDA‐based polyimides could be improved by the introduction of flexible units, nonlinear and non‐coplanar units, and copolymerization. The polyimides with nonlinear and non‐coplanar units derived from 2, 2′, 3, 3′‐BPDA appeared to have prominently enhanced solubility in polar aprotic solvents and polychlorocarbons when compared with the homopolyimide derived from 3, 3′, 4, 4′‐BPDA.     

Chemical modification of 3,3′,4,4′‐biphenyltetracarboxylic dianhydride polyimides by a catechol‐derived bis(ether amine)

Having previously demonstrated that the polyimide derived from 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA) and 1,2‐bis(4‐aminophenoxy)benzene [termed triphenyl ether catechol diamine (TPEC)] exhibited superior tensile properties in addition to good thermal properties, we now provide a preliminary assessment of the properties of the copolyimides prepared from BPDA, TPEC, and another aromatic diamine. The homopolyimides derived from BPDA and many aromatic diamines generally possessed good mechanical properties and thermal properties; however, they were insoluble in available organic solvents. In several cases, organosoluble BPDA copolyimides could be prepared from BPDA and equimolar mixtures of TPEC and another aromatic diamine. All the copolyimides could be formed into tough films with high moduli and strengths and, in most cases, high extensions to break. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 351–358, 2002; DOI 10.1002/app.10342     

Effect of montmorillonite on thermal and moisture absorption properties of polyimide of different chemical structures

The thermal properties and the moisture absorption of three types of polyimide/montmorillonite nanocomposite were investigated: 3,3′,4,4′‐biphenyltetracarboxylic dianhydride‐4,4′‐oxydianiline (BPDA‐ODA); pyromellitic dianhydride‐ODA (PMDA‐ODA); and 3,3′,4,′‐benzophenone tetracarboxylic dianhydride‐ODA (BTDA‐ODA). The inhibition effect on in‐plane coefficients of thermal expansion (CTE) and moisture absorption of these polyimide nanocomposites by layered silicates from montmorillonite was found to decrease with the crystallinity in the pristine polyimides. The largest reduction, 30% in in‐plane CTE occurred in the case of amorphous BTDA‐ODA containing 5 wt % montmorillonite as compared with that of pure BTDA‐ODA, while the reduction in in‐plane CTE was 20% for the case of semicrystalline BPDA‐ODA. The maximum reduction in moisture absorption, 43%, also took place for the case of 3/97 ODA‐Mont/BTDA‐ODA as compared with that of pure BTDA‐ODA, whereas the semicrystalline 1/99 PPD‐Mont/BPDA‐ODA showed a 30% reduction as compared with that of pure BPDA‐ODA. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1742–1747, 2001     

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     

Surface segregation of siloxane containing component in polysiloxane‐block‐polyimide and s‐BPDA/ODA polyimide blends

Surface segregation in polymer blend systems between 3,3′,4,4′‐biphenyltetracarboxylic dianhydride/4,4′‐diaminodiphenyl ether (s‐BPDA/ODA) polyimide and block copolymer based on polysiloxane‐block‐polyimide (SPI) has been investigated. These polyimide blends, having various compositions of the SPI, were processed by a solution casting method. The glass substrate used in the film‐casting process shows significant effect on the migration of surface segregated species to enrich the air‐exposed surface, whereas the more polar s‐BPDA/ODA tends to remain close to the polar glass substrate. X‐ray photoelectron spectroscopy reveals that even at low SPI concentration, the siloxane moieties in the block copolymer tend to segregate into the air side surface. Contact angle measurement evidently indicates an enrichment of the hydrophobic siloxane fraction on the blend film surface. The average water contact angle of glass side surface is 77°C whereas that of the air side is about 102°C in every blend ratio. This behavior confirms the surface segregation phase separation in these polymer blends. Finally, the surface morphology observed by atomic force microscopy also suggests segregation type of phase separation in these blend systems. POLYM. ENG. SCI., 47:489–498, 2007. © 2007 Society of Plastics Engineers.     

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     

Effects of aromatic carboxylic dianhydrides on thermomechanical properties of polybenzoxazine‐dianhydride copolymers

Enhanced thermomechanical properties of bisphenol‐A based polybenzoxazine (PBA‐a) copolymers obtained by reacting bisphenol‐A‐aniline‐type benzoxazine (BA‐a) resin with three different aromatic carboxylic dianhydrides, i.e., pyromellitic dianhydride (PMDA), 3,3′,4,4′ biphenyltetracarboxylic dianhydride (s‐BPDA), or 3,3′,4,4′ benzophenonetetracarboxylic dianhydride (BTDA) were reported. Glass transition temperature (T_g), of the copolymers was found to be in the order of PBA‐a:PMDA>PBA‐a:s‐BPDA>PBA‐a:‐BTDA. The difference in the T_g of the copolymers is related to the rigidity of the dianhydride components. Furthermore, the T_g of PBA‐a:BTDA, PBA‐a:s‐BPDA, and PBA‐a:BTDA films was observed to be significantly higher than that of the neat PBA‐a owing to the enhanced crosslink density by the dianhydride addition. This greater crosslink density results from additional ester linkage formation between the hydroxyl group of PBA‐a and the anhydride group of dianhydrides formed by thermal curing. Moreover, the copolymers exhibit enhanced thermal stability with thermal degradation temperature (T_d) ranging from 410°C to 426°C under nitrogen atmosphere. The char yield at 800°C of the copolymers was found to be remarkably greater than that of the neat PBA‐a with a value up to 60% vs. that of about 38% of the PBA‐a. Toughness of the copolymer films was greatly improved compared to that of the neat PBA‐a. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Synthesis and characterization of benzimidazole‐based low CTE block copolyimides

A series of block and random copolyimide films were synthesized from various molar ratios of two diamines, rigid 2‐(4‐aminophenyl)‐5‐aminobenzimidazole (APBI) and flexible 4,4′‐oxydianiline (ODA) by polycondensation with dianhydride 3,3′,4,4′‐biphenyltetracarboxylic dianhydride. The contents of APBI ranged from 10 to 60 mol % in copolyimides. The copolyimide films obtained by thermal imidization of poly(amic acid) solutions, were characterized by TMA, DMA, TGA, DSC, wide‐angle X‐ray diffraction, FTIR, tensile testing, water uptake (WU), and dielectric constant measurements. Rigid heterocyclic diamine APBI with interchain hydrogen bonding capability, led to low coefficient of thermal expansion (CTE), high T_g, high thermal stability and better mechanical properties. Increasing the APBI mol % caused a gradual decrease in the CTE and increase in T_g, thermal stability and tensile strength properties of the copolyimides films. Moreover, significantly enhanced thermal and mechanical properties of the block copolyimides were also found as compared to random copolyimides. The block copolyimide with APBI content of 60 mol %, achieved excellent properties, that is, a low CTE (4.7 ppm/K), a high T_g at 377°C, 5% weight loss at 562°C and a tensile strength at 198 MPa. This can be interpreted because of comparatively higher degree of molecular orientation in block copolyimides. These copolyimides also exhibited better dielectric constant and WU. This combination of properties makes them attractive candidates for base film materials in future microelectronics. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Syntheses and properties of polyimides derived from diamines containing 2,5‐disubstituted pyridine group

A series of novel homo‐ and copolyimides containing pyridine units were prepared from the heteroaromatic diamines, 2,5‐bis (4‐aminophenyl) pyridine and 2‐(4‐aminophenyl)‐5‐aminopyridine, with pyromelltic dianhydride (PMDA), and 3,3′, 4,4′‐biphenyl tertracarboxylic dianhydride (BPDA) via a conventional two‐step thermal imidizaton method. The poly(amic acid) precursors have inherent viscosities of 1.60–9.64 dL/g (c = 0.5 g/dL in DMAC, 30°C) and all of them can be cast and thermally converted into flexible and tough polyimide films. All of the polyimides show excellent thermal stability and mechanical properties. The polyimides have 10% weight loss temperature in the range of 548–598°C in air. The glass transition temperatures of the PMDA‐based samples are in the range of 395–438°C, while the BPDA‐based polyimides show two glass transition temperatures (T_g1 and T_g2), ranging from 268 to 353°C and from 395 to 418°C, respectively. The flexible films possess tensile modulus in the range of 3.42–6.39 GPa, strength in the range of 112–363 MPa and an elongation at break in the range of 1.2–69%. The strong reflection peaks in the wide‐angle X‐ray diffraction patterns indicate that the polyimides have a high packing density and crystallinity. The polymer films are insoluble in common organic solvents exhibiting high chemical resistance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1844–1851, 2006     

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     

Synthesis and properties of novel alicyclic‐functionalized polyimides prepared from natural—(D)‐camphor

In this article, a new alicyclic‐functionalized diamine, 1,3‐bis(4‐aminophenoxymethylene)‐1,2,2‐trimethylclopentane (BAMT) was successfully synthesized starting from natural —(D)‐camphor through four reaction steps of oxidation to offer a dicaboxylic acid, reduction to offer a diol, nucleophilic substitution to give a dinitro compound and then reduction to give the final diamine. Two alicyclic‐containing polyimides were prepared by polycondensing BAMT with 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA) and 4,4′‐oxydiphthalicanhydride (ODPA), respectively. For the studies of the structure–property relationships of the polyimides, one aromatic polyimide of 4, 4′‐oxydianiline (ODA) polycondensed with ODPA was prepared in comparison. The alicyclic‐containinig polyimides PI (BPDA‐BAMT) and PI (ODPA‐BAMT) maintain good thermal properties with glass transition temperatures (T_g) of 257°C and 240°C, and temperatures at 5% weight loss (T₅) of 443°C and 436°C in nitrogen, respectively. The alicyclic polyimides exhibit tensile strengths of 91.9–133 MPa, Young's moduli of 2.75—3.24 GPa, and elongations at break of 5.6–18%. Compared with the aromatic polyimide PI (ODPA‐ODA), PI (ODPA‐BAMT) shows improved transparency with the UV‐Vis transmittance at 500 nm over 80%. In addition, PI (ODPA‐BAMT) displays better solubility than PI (ODPA‐ODA), which has been confirmed by the bigger d‐spacing value of PI (ODPA‐BAMT) than that of PI (ODPA‐ODA) calculated from the Wide‐angle X‐ray Diffraction spectra. This study indicates that the renewable forestry compound, such as natural —(D)‐camphor, could be a good origin for the structural designing and preparation of alicyclic‐containing polyimides with outstanding combined features suitable for advanced microelectronic and optoelectronic applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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     

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     

Structure–property relationship of polyimide fibers containing ether groups

The copolyimide (co‐PI) fibers with outstanding mechanical properties were prepared by a two‐step wet‐spinning method, derived from the design of combining 4,4′‐oxydianiline (ODA) with the rigid 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA)/p‐phenylenediamine (p‐PDA) backbone. The mechanical properties of PI fibers were drastically improved with the optimum tensile strength of 2.53 GPa at a p‐PDA/ODA molar ratio of 5/5, which was approximately 3.7 times the tensile strength of BPDA/p‐PDA PI fibers. Two‐dimensional wide‐angle X‐ray diffraction indicated that the highly oriented structures were formed in the fibers. Two‐dimensional small‐angle X‐ray scattering revealed the existence of the needle‐shaped microvoids aligned parallel to the fiber axis, and the introduction of ODA led to the reduction in the size of the microvoids. As a result, the significantly improved mechanical properties of PI fibers were mainly attributed to the gradually formed homogeneous structures. The co‐PI fibers also exhibited excellent thermal stabilities of up to 563°C in nitrogen and 536°C in air for a 5% weight loss and glass transition temperatures above 279°C. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42474.     

Preparations and properties of a high performance semicrystalline copolyimide and composites reinforced with glass fiber

A semicrystalline copolyimide derived from 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (s‐BPDA), 1,3‐bis‐(4‐aminophenoxy)benzene (TPER), and 4,4′‐oxydianiline (4,4′‐ODA), end capped with phthalic anhydride (PA), was synthesized. Glass fiber reinforced composite was also prepared by impregnating powdery glass fiber with poly(amic acid) followed by solution imidization techniques. This copolyimide displayed a glass transition temperature of 202°C and a melting temperature of 373°C by differential scanning colorimeter (DSC). Crystallization and melting behaviors were investigated under nonisothermal and isothermal crystallization conditions. Double exothermic peaks were found by DSC when the copolyimide was cooled from the melt and multiple melting behaviors can be observed after the coployimide had been isothermally crystallized at different temperatures. Mechanical properties were investigated by dynamical mechanical analysis (DMA) and tensile experiments. The samples were cured at different temperatures and then tested at different temperatures. Results indicated that the copolyimide and the composite showed excellent mechanical properties. Additionally, this copolyimide also showed lower melt viscosity by rheological analysis. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40345.     

Synthesis of a new siloxane‐containing alicyclic dianhydride and the derived polyimides with improved solubility and hydrophobicity

The structural transformation strategy of cis‐5‐norbornene‐endo‐2,3‐dicarboxylic anhydride (NA) was performed by esterification. The double bond on the diester of NA showed adequate hydrosilylation reactivity with Si? H bonds of phenyl‐containing disiloxane. Thereby, a new siloxane‐containing alicyclic dianhydride, 5,5′‐exo‐(1,3‐dimethyl‐1,3‐diphenyl‐disiloxane‐1,5‐diyl)bisbicyclo[2,2,1]heptane‐2,3‐endo‐dicarboxylic anhydride 6 was successfully synthesized starting from NA, 1,3‐dimethyl‐1,3‐diphenyldisiloxane and platinum complex catalyst. The whole synthetic route of dianhydride 6 consisted of esterification, hydrosilylation, saponification, acidification, and dehydration. A series of polyimides (PIs) were prepared from dianhydride comonomers of 6 and 4,4′‐biphenyltetracarboxylic dianhydride (BPDA) in different molar ratio together with the diamine 4,4′‐oxydianiline (ODA). The thermal and mechanical properties of PIs showed somewhat decrease with increasing content of dianhydride 6. The solubility of PIs increased with the increasing content of dianhydride 6, and further calculation from Bragg's equation indicated that average interchain distance (d‐spacing value) increased with increasing content of siloxane and alicyclic segments in the backbone of PIs. It was revealed that the hydrophobicity of PIs increased with the increasing content of dianhydride 6 . Polyimide 7g , which was prepared from 100% 6 and ODA, showed water adsorption of less than 0.7% and contact angle against water of 101.1°. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci., 2013     

Modification of cyanate ester resin by soluble polyimides

Soluble polyimides (PIs) were prepared as random or multiblock types with 4,4′‐(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (s‐BPDA) as acid dianhydride components and 4,4′‐bis(m‐aminophenoxy) diphenyl sulfone (m‐BAPS) as a diamine component by a one‐pot process and used to improve the brittleness of the cyanate ester resin. Random‐type PIs were more effective as modifiers than multiblock‐type PIs. The morphologies of the modified resins depended on PI structure, molecular weight, and concentration. The most effective modification of the cyanate ester resin was attained because of a heterogeneous phase structure composed of a flat matrix phase and phase‐inverted structures of the modified resin; a 15 wt % inclusion of a random PI (weight‐average molecular weight = 63,400) composed of 6FDA, s‐BPDA, and m‐BAPS (0.5/0.5/1.0 molar ratio) led to a 65% increase in the fracture toughness for the modified resin with a slight loss of flexural strength and a retention of flexural modulus and glass‐transition temperature, compared with the values for the unmodified resin. Water absorptivity of the modified resin was comparable to that of the unmodified resin up to 400 h, and then, water absorption of the modified resins increased considerably. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1–11, 2003     

Properties of copolyimides prepared from different tetracarboxylic dianhydrides and diamines

Various copolymides were prepared from two acid dianhydrides (BPDA, 3,3′,4,4′-biphenyl tetracarboxylic dianhydride; PMDA, pyromelitic dianhydride) and two diamines (PPD, p-phenylene diamine; ODA, 4,4′-oxydianiline). The thermal and mechanical properties of these polyimides were examined in detail. By appropriately selecting the ratios of the acid dianhydride component and the diamine component, polyimide films having desirable mechanical and thermal characteristics can be obtained. Further, it was proved that there is a correlation between the properties and the compositions of the copolyimides and that the properties could be estimated from the compositions by the use of multiple regression analysis. © 1996 John Wiley & Sons, Inc.     

Organosoluble polyimides derived from asymmetric 2‐substituted‐and 2,2′,6‐trisubstituted‐4,4′‐oxydianilines

We report a new method for the preparation of asymmetric diamines using 4,4′‐oxydianiline (4,4′‐ODA) as the starting material. By controlling the equivalents of bromination agent, N‐bromosuccinimide, we were able to attach bromide and phenyl substituents at the 2‐ or 2,2′,6‐positions of 4,4′‐ODA. Thus, four new asymmetric aromatic diamines, 2‐bromo‐4,4′‐oxydianiline (6), 2,2′,6‐tribromo‐4,4′‐oxydianiline (7), 2‐phenyl‐4,4′‐oxydianiline (8) and 2,2′,6‐triphenyl‐4,4′‐oxydianiline (9), were synthesized by this method. Their structural asymmetry was confirmed using ¹H NMR spectroscopy. Asymmetric polyimides (PI10–PI13) were prepared from these diamines and three different dianhydrides (pyromellitic dianhydride (PMDA), 3,3′,4,4′‐biphenyltetracarboxylic dianhydride and 2,2‐bis(3,4‐dicarboxyphenyl)hexafluoropropane dianhydride) in refluxing m‐cresol. The formed polyimides, except PI10a derived from 6 and PMDA, were all soluble in m‐cresol without premature precipitation during polymerization. These polyimides with inherent viscosity of 0.41–0.96 dL g^?1, measured at a concentration of 0.5 g dL^?1 in N‐methyl‐2‐pyrrolidone at 30 °C, can form tough and flexible films. Because of the structural asymmetry, they also exhibited enhanced solubility in organic solvents. Especially, polyimides PI11a and PI13a derived from 7 and 9 with rigid PMDA were soluble in various organic solvents at room temperature. The structural asymmetry of the prepared polyimides was also evidenced from ¹H NMR spectroscopy. In the ¹H NMR spectrum of PI11a, the protons of pyromellitic moiety appeared in an area ratio of 1:2:1 at three different chemical shifts, which were assigned to head‐to‐head, head‐to‐tail and tail‐to‐tail configurations, respectively. These polyimides also exhibited good thermal stability. Their glass transition temperatures ranged from 297 to 344 °C measured using thermal mechanical analysis. © 2013 Society of Chemical Industry     

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