Gas‐sorption properties of 6FDA–durene/1,4‐phenylenediamine (pPDA) and 6FDA–durene/1,3‐phenylenediamine (mPDA) copolyimides

We investigated the sorption isotherms of O₂, N₂, CH₄, and CO₂ gases in 6FDA–durene, 6FDA–1,4‐phenylenediamine (6FDA–pPDA), and 6FDA–1,3‐phenylenediamine (6FDA–mPDA) homopolymers and 6FDA–durene/pPDA and 6FDA–durene/mPDA copolyimides. The solubilities decrease in the order of the inherent condensabilities of the penetrant gases, namely, CO₂, CH₄, O₂, and N₂. The chemical structures of the polymer, as well as the chain packing, determine the sorption properties of these homopolymers and copolymers. The FDA–durene homopolymer has the highest solubility for all gases because of its high specific free volume and fractional free volume. The solubilities of the copolymers increase with an increasing 6FDA–durene content, while the solubility selectivities of the copolymers only vary slightly. The values of K_D (Henry's law constant) and C_H′ (Langmuir site capacity) of these copolyimides decrease with a decreasing 6FDA–durene content. To our surprise, contradictory to the previous known fact that the meta‐connected materials tend to have denser molecular packing than that of the para‐linked materials for homopolymers, the 6FDA–durene/mPDA 80/20 copolymer has higher gas solubilities than those of the 6FDA–durene/pPDA 80/20 copolymer. The random moiety sequence within the copolymer may be the main cause for the abnormal phenomenon. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2187–2193, 2003     

Polycarbonate/1‐(2‐hydroxyethyl)‐2,3‐dimethylimidazolium chloride composite membranes and short‐range chain mobility analysis

In this investigation, the incorporation of imidazolium salt, 1‐(2‐hydroxehtyl)‐2,3‐dimethylimidazolium chloride [hydemmim][Cl] within bisphenol A polycarbonate (PC) matrix and the subsequent formation of membranes via casting were studied. Characterizations that aimed to establish structure‐property correlations by Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, dynamic mechanical thermal analysis, and water vapor transport (WVT) were performed. The results indicated that the presence of ionic liquid (IL) within the PC matrix significantly alter the local and macromolecular structure. The thermal stability is increased for all levels of incorporation. The plasticizing and antiplasticizing effects were observed due to the influence of the proportions of IL incorporated and of the cation's substituent chain of this IL. Distinct mechanisms of WVT were also observed in the presence of IL. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45117.     

Structure and properties of aromatic poly(benzimidazole‐imide) copolymer fibers

A series of co‐polyimide fibers were prepared by thermal imidization of copolyamic acids derived from 3,3′,4,4′‐biphenyltertracarboxylic dianhydride (BPDA) and pyromellitic dianhydride (PMDA) in various molar ratios with 2‐(4‐aminophenyl)?5‐aminobenzimidazole (BIA). The dynamic mechanical behaviors of these polyimide (PI) fibers revealed that the glass transition temperature (T_g) was significantly improved upon increasing PMDA content. Heat‐drawing process led to dramatic change on the glass transition behavior of BPDA/BIA system, but had a small impact on BPDA/PMDA/BIA co‐polyimide fibers. This difference for PI fibers is attributed to the different degree of ordered structure of the fibers affected by heat‐drawing. The incorporation of PMDA obviously improved the dimensional stability against high temperature, due to the restricted movement of polymer chains. In addition, the obtained fibers show excellent mechanical and thermal properties because of the strong hydrogen bonding due to the incorporation of benzimidazole moieties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41474.     

Effect of thermal hysteresis on the gas permeation properties of 6FDA‐based polyimides

The effect of thermal hysteresis on the polymer chain packing and permeation properties of two 6FDA‐based polyimide isomers was investigated. Thermal quenching resulted in a small increase in the fractional free volume of the polyimides with respect to the samples that had been annealed. Quenching from above the glass‐transition temperature also resulted in larger increases in the permeabilities for both 6FDA–6FmDA and 6FDA–6FpDA with respect to annealed samples. Meta‐connected 6FDA–6FmDA exhibited a larger increase in the permeability after quenching than the para‐connected isomer, 6FDA–6FpDA. This larger increase in the permeability for 6FDA–6FmDA may have been due to differences in the effects of the increases in the free volume on the intersegmental resistance to chain motions. Although physical aging over a 3‐month period resulted in a reduction in the permeability of quenched samples of 6FDA–6FpDA, the quenched samples maintained higher permeabilities than the annealed samples. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1174–1182, 2004     

Amphiphilic diblock copolymers poly(2‐hydroxyethylmethacrylate)‐b‐(N‐phenylmaleimide) and poly(2‐hydroxyethylmethacrylate)‐b‐(styrene) using the macroinitiator poly(HEMA)‐Cl by ATRP: Preparation,characterization, and thermal properties

In recent years, much attention has been given to the development of specialty polymers from useful materials. In this context, amphiphilic block copolymers were prepared by atom transfer radical polymerization (ATRP) of N‐phenylmaleimide (N‐PhMI) or styrene using a poly(2‐hydroxyethylmethacrylate)‐Cl macroinitiator/CuBr/bipyridine initiating system. The macroinitiator P(HEMA)‐Cl was directly prepared in toluene by reverse ATRP using BPO/FeCl₃ 6 H₂O/PPh₃ as initiating system. The microstructure of the block copolymers were characterized using FTIR, ¹H‐NMR, ¹³C‐NMR spectroscopic techniques and scanning electron microscopy (SEM). The thermal behavior was studied by differential scanning calorimetry (DSC), and thermogravimetry (TG). The theoretical number average molecular weight (M_n,th) was calculated from the feed capacity. The microphotographs of the film's surfaces show that the film's top surfaces were generally smooth. The TDT of the block copolymer P(HEMA)₈₀‐b‐P(N‐PhMI)₂₀ and P(HEMA)₉₀‐b‐P(St)₁₀ of about 290°C was also lower than that found for the macroi′nitiator poly(HEMA)‐Cl. The block copolymers exhibited only one T_g before thermal decomposition, which could be attributed to the low molar content of the N‐PhMI or St blocks respectively. This result also indicates that the phase behavior of the copolymers is predominately determined by the HEMA block. The curves reveal that the polymers show phase transition behavior of amorphous polymers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Phototransparency and water vapor sorption properties of ABA‐type triblock copolymers derived from 6FDA‐TeMPD and poly(2‐methyl‐2‐adamantylmethacrylate)

The phototransparency and water vapor sorption properties of ABA‐type triblock copolymer membranes derived from 4,4‐(hexafluoroisopropylidene) diphthalic anhydride‐2,3,5,6‐tetramethyl‐1,4‐phenylenediamine (PI) and poly(2‐methyl‐2‐adamantylmethacrylate) (PMAdMA) were investigated, with focus on the effect of the adamantane component. The phototransparency of PMAdMA‐block‐PI‐block‐PMAdMA [Block(PI/PMAdMA)] was about 10–20% higher than that of poly(methyl methacrylate)‐block‐PI‐block‐Poly(methylmethacrylate) [Block(PI/PMMA)] because the high symmetric structure of adamantane inhibited photoabsorbance. The water vapor solubility of Block(PI/PMAdMA) decreased with increased PMAdMA because the PMAdMA had a hydrophobic property. Interestingly, in all relative‐pressure regions, Block(PI/PMAdMA) with the least PMAdMA content showed a higher solubility coefficient than PI because the high mobility of PMAdMA in Block(PI/PMAdMA) resulted in additional sorption sites in the PI segment. A comparison of Block(PI/PMAdMA) with Block(PI/PMMA) in terms of relative pressure at the beginning of clustering further revealed that cluster formation in Block(PI/PMAdMA) was inhibited compared with Block(PI/PMMA) because bulky structure of adamantane restricted the mobility of the polymer main chain. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43795.     

Dielectric and gas transport properties of the films of thermally stable poly(arylene ether ketone)s containing content‐tunable benzimidazole moiety

A series of thermally stable poly(arylene ether ketone)s (PAEKs) bearing benzimidazole structure in the main chains, named poly(arylene ether ketone‐benzimidazole)s (PAEK‐BIs), were directly synthesized by polycondensation of dimethyl bisphenol, dibenzimidazole bisphenol, and difluorobenzophenones. By systematically varying the amount ratio of two kind of bisphenols, the content of benzimidazole moiety in the backbone was controlled straightforwardly. The prepared amorphous polymers were characterized in terms of Fourier transform infrared spectroscopy, proton nuclear magnetic resonance, thermal, dielectric, and gas transport properties. Evaluation of solubility reveals that PAEK‐BIs with >60% content of benzimidazole units could be soluble in commonly used organic solvents. Also polymers containing content‐tunable benzimidazole show high glass‐transition temperatures (T_g's, 157–319°C) and excellent thermal stability (e.g., temperature of 5% weight loss, above 438°C in air). Dielectric constants of PAEK‐BIs measured at 25°C are all less than 2.66 in the frequency range of 0.1–50 kHz. For dense films, the ideal gas selectivity and permeability coefficients could be compared with that of commercial Ultem 1000 membrane, which indicate that the PAEK‐BIs are potential to be used for gas separation membrane material. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41289.     

Synthesis of a poly(methyl methacrylate)‐b‐poly[2‐(N,N‐dimethylamino) ethyl methacrylate] block copolymer and its effects on the surface charges and pH‐responsive properties of poly(vinylidene fluoride) blend membranes

A poly(methyl methacrylate) (PMMA)‐b‐poly[2‐(N,N‐dimethylamino) ethyl methacrylate] (PDMAEMA) block copolymer was successfully synthesized by a reversible addition–fragmentation chain‐transfer method. The resulting copolymer was used to prepare poly(vinylidene fluoride) blend membranes via a phase‐inversion technique. The polymorphism, structure, and properties of the blend membranes were investigated by Fourier transform infrared spectrometry, scanning electron microscopy (SEM), ζ potential analysis, and filtration. The results indicate that PMMA‐b‐PDMAEMA could migrate onto the surface of the membrane during the coagulation process, and more of the β‐crystal phase appeared with the increase of the block copolymer in the membranes. The surface morphology and cross section of the membranes were also affected by the copolymer, as shown by SEM. The ζ‐potential results show that the surface charges of the membrane could be changed from positive to negative at an isoelectric point as the pH increased. The blend membrane also exhibited good pH sensitivity, and its water flux showed a great dependence on pH. The filtration experiment also indicated that the blend membrane had good hydrophilicity and antifouling properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40685.     

Microwave assisted glycolysis of poly(ethylene terephthalate) catalyzed by 1‐butyl‐3‐methylimidazolium bromide ionic liquid

The combination of ionic liquid (IL) associated with microwave energy may have some potential application in the chemical recycling of poly (ethylene terephthalate). In this processes, glycolysis of waste poly (ethylene terephthalate) recovered from bottled water containers were thermally depolymerized with solvent ethylene glycol (EG) in the presence of 1‐butyl‐3‐methyl imidazolium bromide ([bmim]Br) as catalyst (IL) under microwave condition. It was found that the glycolysis products consist of bis (2‐hydroxyethyl) terephthalate (BHET) monomer that separated from the catalyst IL in pure crystalline form. The conversion of PET reach up to 100% and the yield of BHET reached 64% (wt %). The optimum performance was achieved by the use of 1‐butyl‐3‐methyl imidazolium bromide as a catalyst, microwave irradiations temperature (170–175°C) and reaction time 1.75–2 h. The main glycolysis products were analyzed by ¹H NMR, ¹³C NMR, LC‐MS, FTIR, DSC, and TGA. When compared to conventional heating methods, microwave irradiation during glycolysis of PET resulted in short reaction time and more control over the temperature. This has allowed substantial saving in energy and processing cost. In addition, a more efficient, environmental‐friendly, and economically feasible chemical recycling of waste PET was achieved in a significantly reduced reaction time. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41666.     

Molecular simulation of the glass transition and proton conductivity of 2,2′‐benzidinedisulfonic acid and 4,4′‐diaminodiphenylether‐2,2′‐disulfonic acid‐based copolyimides as polyelectrolytes for fuel cell applications

The glass transition temperatures (T_gs) and proton conductivities of polyimides synthesized from naphthalene‐1,4,5,8‐tetracarboxylic dianhydride (NTDA), 2,2′‐benzidinedisulfonic acid (BDSA), 4,4′‐diaminodiphenylether‐2,2′‐disulfonic acid (ODADS), and non‐sulfonated diamine monomers have been predicted using molecular dynamics simulations. The specific volumes for two dry and four hydrated NTDA‐based polyimides were plotted versus temperatures above and below T_gs to obtain the glass transition temperatures. The simulation results suggest that the ODADS‐based polyimide membranes exhibit lower T_gs and thus better mechanical properties than the BDSA‐based polyimides, which may be attributed to the high mobility of backbones of ODADS as supported by the vectorial autocorrelation function (VACF) results of this study. In addition, comparison of the simulated T_gs for the dry and hydrated ODADS‐based polyimides has shown that water content in polyimides can affect their T_gs. The proton conductivities of a representative polyimide in both dry and hydrated conditions have been obtained from molecular dynamics simulations of the proton and hydronium ion diffusion. The simulated conductivity for the hydrated NTDA‐ODADS/BAPB cell is in reasonable agreement with the experimental value obtained from the AC impedance method. The relationship between the chemical composition, chain flexibility, and the glass transition and proton conduction of these NTDA‐based polyimides was explored on the basis of VACF and pair correlation function analysis. Copyright © 2006 Society of Chemical Industry     

Preparation and pervaporation performance of 3,3‐bis[4‐(4‐aminophenoxy)phenyl] phthalide based polyimide membranes

A series of novel solvent‐soluble polyimides based on the diamine of 3,3‐bis[4‐(4‐aminophenoxy)phenyl] phthalide (BAPP) were prepared. The effects of the dianhydride structures on the pervaporation performance of aqueous alcohol mixtures through these polyimide membranes were studied. The BAPP‐based polyimide membranes exhibited water permselectivity during all process runs. The permeation rate increased with the addition of bulky groups to the polyimide backbone. The effects of the feed solution concentration, feed solution temperature, and carbon atom number of the feed alcohol on the pervaporation performance were also investigated systematically. Optimum pervaporation results, a separation factor of 22 and a permeation rate of 270 g/m² h, were obtained for a 90 wt % feed aqueous ethanol solution through a 3,3′,4,4′‐biphenyl tetracarboxylic dianhydride polyimide membrane at 25°C. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2046–2052, 2005     

Bis[4‐(4‐maleimidephen‐oxy)phenyl]propane/N,N‐4,4′‐bismaleimidodiphenylmethyene blend modified with diallyl bisphenol A

In this article, 2,2′‐bis[4‐(4‐maleimidephen‐oxy)phenyl)]propane (BMPP) resin and N,N‐4,4′‐bismaleimidodiphenylmethyene (BDM) resin blends were modified by diallyl bisphenol A (DABPA). The effects of the mole concentration of BMPP on mechanical properties, fracture toughness, and heat resistance of the modified resins were investigated. Scanning electron microscopy was used to study the microstructure of the fractured modified resins. The introduction of BMPP resin improves the fracture toughness and impact strength of the cured resins, whose thermal stabilities are hardly affected. Dynamic mechanical analysis shows that the modified resins can maintain good mechanical properties at 270.0°C, and their glass transition temperatures (T_g) are above 280.0°C. When the mole ratio of BDM : BMPP is 2 : 1(Code 3), the cured resin performs excellent thermal stability and mechanical property. Its T_g is 298°C, and the Charpy impact strength is 20.46 KJ/m². The plane strain critical stress intensity factor (K_IC) is 1.21 MPa·m^0.5 and the plane strain critical strain energy release rate (G_IC) is 295.64 J/m². Compared with that of BDM/DABPA system, the K_IC and G_IC values of Code 3 are improved by 34.07% and 68.10%, respectively, which show that the modified resin presented good fracture toughness. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40395.     

Structure and properties of polyimide‐g‐nylon 6 and nylon 6‐b‐polyimide‐b‐nylon 6 copolymers

Polyimide‐g‐nylon 6 copolymers were prepared by the polymerization of phenyl 3,5‐diaminobenzoate with several diamines and dianhydrides with a one‐step method. The polyimides containing pendant ester moieties were then used as activators for the anionic polymerization of molten ε‐caprolactam. Nylon 6‐b‐polyimide‐b‐nylon 6 copolymers were prepared by the use of phenyl 4‐aminobenzoate as an end‐capping agent in the preparation of a series of imide oligomers. The oligomers were then used to activate the anionic polymerization of ε‐caprolactam. In both the graft and copolymer syntheses, the phenyl ester groups reacted quickly with caprolactam anions at 120°C to generate N‐acyllactam moieties, which activated the anionic polymerization. All the block copolymers had higher moduli and tensile strengths than those of nylon 6. However, their elongations at break were much lower. The graft copolymers based on 2,2′‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]propane dianhydride and 2,2′‐bis[4‐(4‐aminophenoxy)phenyl]propane displayed elongations comparable to that of nylon 6 and the highest moduli and tensile strengths of all the copolymers. The thermal stability, moisture resistance, and impact strength were dramatically increased by the incorporation of only 5 wt % polyimide into both the graft and block copolymers. The graft and block copolymers also exhibited improved melt processability. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 300–308, 2006     

Glass‐transition and gas‐transport characteristics of polymer nanocomposites based on crosslinked poly(ethylene oxide)

The glass‐transition and gas‐transport properties of rubbery polymer nanocomposites based on crosslinked poly(ethylene oxide) and metal oxide nanoparticles were studied. Nanocomposite samples were prepared by the UV photopolymerization of poly(ethylene glycol) diacrylate (n ～ 14) in the presence of magnesium oxide or silica nanoparticles. The thermomechanical properties of the composites were investigated with dynamic mechanical and dielectric spectroscopy methods. The inclusion of nanoparticles in the crosslinked poly(ethylene glycol) diacrylate network led to a systematic increase in rubbery modulus and a modest positive offset (～6°C) in the measured glass‐transition temperature for both systems. Bulk density measurements indicated only minimal void volume fraction in the composites, and CO₂ and light gas permeability decreased with particle loading; for example, the CO₂ infinite dilution permeability at 35°C decreased from 106 barrer in the unfilled polymer to 55 barrer in a nanocomposite containing 30 wt % magnesium oxide nanoparticles. The inclusion of toluene diluent in the prepolymerization mixtures produced a limited enhancement in sample permeability, but the sizeable increases in gas transport with particle loading reported for certain other rubbery nanocomposite systems were not realized in the crosslinked poly(ethylene glycol) diacrylate composites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Copolymerization of N‐(4‐carboxyphenyl) itaconimide or N‐(4‐carboxyphenyl) itaconamic acid with methyl methacrylate

This paper describes the synthesis and characterization of N‐(4‐carboxyphenyl) itaconamic acid (CPA) and N‐(4‐carboxyphenyl) itaconimide (CPI) obtained by reacting itaconic anhydride with p‐aminobenzoic acid. Structural and thermal characterization of CPA and CPI was done using ¹H‐NMR, FTIR, and differential scanning calorimetry (DSC). Copolymerization of CPA or CPI with methyl methacrylate (MMA) in solution was carried out at 60 °C using azobisisobutyronitrile as an initiator and dimethyl acetamide or THF as solvent. Feed compositions having varying mole fractions of CPA or CPI ranging from 0.05–0.20 or 0.1–0.5 were taken to prepare copolymers. Copolymerizations were terminated at low percentage conversion. Structural characterization of copolymers was done by ¹H‐NMR and elemental analysis. Copolymer composition was determined using percentage nitrogen content. The reactivity ratios were r₁ (MMA) = 0.68 ± 0.06 and r₂ (CPI) = 0.46 ± 0.06. The intrinsic viscosity [η] was determined using an Ubbelohde suspension level viscometer. [η] decreased with increasing mole fraction of N‐(p‐carboxyphenyl) itaconimide or N‐(p‐carboxyphenyl) itaconamic acid in copolymers. Glass transition temperature and thermal stability of the copolymers were determined using DSC and thermogravimetric analysis, respectively. The glass transition temperature (T_g) as determined from DSC scans increased with increasing amounts of CPA or CPI in copolymers. A significant improvement in the char yield was observed upon copolymerization. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1909–1915, 2005     

Effect of 1‐butyl‐3‐methylimidazolium iodide containing electrospun poly(vinylidene fluoride‐co‐hexafluoropropylene) membrane electrolyte on the photovoltaic performance of dye‐sensitized solar cells

Electrospun poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVdF‐HFP) membrane was prepared from a solution of 16 wt % of PVdF‐HFP containing acetone/N,N‐dimethyl acetamide (7:3 wt %). The prepared electrospun PVdF‐HFP membrane (esPM) was then soaked in ionic liquid electrolyte containing 0.5M LiI, 0.05M I₂ , and 0.5M 4‐tert butylpyridine, 0.5M 1‐butyl‐3‐methylimidazolium iodide (BMImI) in acetonitrile to get electrospun PVdF‐HFP membrane electrolyte (esPME). The effect of various concentrations of BMImI containing esPME on ionic conductivity was studied by AC‐impedance measurements and the diffusion co‐efficients was determined by linear sweep voltammetry. The photovoltaic performance of a DSSC fabricated using 0.5M BMImI containing electrospun PVdF‐HFP membrane electrolyte (0.5M BMImI‐esPME) has power conversion efficiency (PCE) of 6.42%. But the stability of the DSSC fabricated using 0.5M BMImI‐esPME was considerably superior to that fabricated using 0.5M BMImI containing liquid electrolyte (0.5M BMImI‐LE). © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42032.     

Synthesis and characterization of sulfonated block copolyimides derived from 4,4'‐sulfide‐bis(naphthalic anhydride) for proton exchange membranes

A series of sulfonated copolyimides (SPIs) with hydrophilic segment length of 20–60 based on 4,4′‐sulfide‐bis(naphthalic anhydride) (SBNA) have been successfully synthesized to improve hydrolytic stability and proton conductivity. The SPI membranes were cast from their m‐cresol solutions, and they were characterized by determining the water uptake, water swelling ratio, mechanical properties, hydrolytic stability, oxidative stability, and proton conductivity. It was found that the water uptake of SPI membranes was low and decreased as the hydrophilic segment length increased, which led to good dimensional stability. In addition, the SPI membranes with low ion‐exchange capacity (IEC) value displayed excellent hydrolytic stability and retained good mechanical properties even after harsh hydrolysis testing, in which the block SPI with hydrophilic segment length of 40 had the best hydrolytic stability, while those with high IEC value showed an apparent decrease. All of the block SPI membranes show better conductivity than the random ones at the temperature range from 30 to 70°C. Interestingly, the proton conductivities of random SPI membranes were higher than that of corresponding block ones at 90°C. The block SPI with hydrophilic segment length of 40 gave the highest proton conductivity as the temperature increased among the block SPIs. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41501.     

Copolymers of Poly(2,5‐benzimidazole) and Poly[2,2′‐(p‐phenylene)‐5,5′‐bibenzimidazole] for High‐Temperature Fuel Cell Applications

Copolymers of poly(2,5‐benzimidazole) (ABPBI) and poly[2,2′‐(p‐phenylene)‐5,5′‐bibenzimidazole] (pPBI) were synthesized for use as fuel cell membranes to take advantage of the properties of both constituents. The composition of the copolymers were controlled by changing the feed ratio of 3,4‐diaminobenzoic acid and terephthalic acid with 3,3′‐diaminobenzidine in the polycondensation reaction. The copolymer membranes showed higher conductivities, better mechanical properties, and larger acid absorbing abilities than commercial poly[2,2′‐(m‐phenylene)‐5,5′‐bibenzimidazole] membranes.

     

Synthesis and properties of 6FDA‐BisAAF‐PPD copolyimides for microelectronic applications

In this work, fluorine‐containing copolyimides were synthesized from 6FDA dianhydride and different ratios of BisAAF and PPD diamines. Properties, such as composition, viscosity, dielectric constant, glass‐transition temperature, thermal decomposition temperature, tensile characteristics, and transmittance, were investigated by using elemental analysis, viscometry, Fourier transform infrared spectrometry, differential scanning calorimetry, a thermogravimetric analyzer, a tensile tester, and UV–visible spectrophotometry. After curing at 300°C for 1 h, imidization was observed, as indicated the appearance of an absorption peak of the carbonyl of the imide at 1780 cm^?1 (C?O asymmetry stretching). The inherent viscosity increased with an increasing PPD mole fraction, from 0.40 dL/g of pure 6FDA‐BisAAF to 0.84 dL/g of pure 6FDA‐PPD. The dielectric constant decreased with increasing fluorine content. The glass‐transition temperature increased with an increasing PPD mole fraction; the values increased from 317°C with pure 6FDA‐BisAAF polyimide to 364°C with pure 6FDA‐PPD polyimide. The 5% weight loss temperature (T_d) of the copolyimides was around 530°C in air and 540°C in a nitrogen atmosphere. The tensile modulus and tensile strength gradually increased with an increasing PPD molar fraction. The transmittance of 6FDA‐BisAAF‐PPD copolyimides was greater than 90% at wavelengths above 500 nm. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2064–2069, 2005