Effect of metal halides on thermal,mechanical, and electrical properties of polypyromellitimide films

This paper describes the effect of metal halides (Co²⁺, Sn²⁺, and Hg²⁺) on the properties of polyimides. Low temperature, solution polycondensation reaction of pyromellitic dianhydride and 4,4′-diaminodiphenyl ether was used for preparation of a poly(amide-acid) solution in dimethylformamide ([η] = 2.0 dL/g). Films containing 1% (w/w) of cobalt (II) chloride, tin (II) chloride, and mercury (II) chloride were prepared by solution casting of poly(amide-acid) from the DMF solution. Cyclodehydration to polyimide was done by heating the films in nitrogen atmosphere for one hour each at 100°, 200°, and 250°C. The color of the films depended on the dopant and was yellow (HgCl₂ or SnCl₂) or green (CoCl₂) Higher percentage weight loss was observed in doped films in nitrogen atmosphere in the temperature range of 250–400°C. No significant difference in thermal behavior of doped and undoped films was observed above 500°C. Doping reduced the tensile strength of polyimide films, maximum reduction was observed in CoCl₂-doped film. The electrical conductivity of polyimide films as a function of temperature and field was studied. Undoped polyimide showed ohmic behavior up to 150°C. In doped films at lower voltages Poole-Frenkel mechanism was operative, while at high voltages Richardson-Schottky's mechanism was operative. Dielectric relaxation in polyimide films was also studied.     

Silver–polyimide nanocomposite membranes: Macromolecular‐matrix‐mediated metallization of an aromatic,fluorinated polyimide yielding highly reflective films at low metal concentrations

Highly reflective, surface‐metalized, flexible polyimide films were prepared by the incorporation of a soluble silver‐ion complex, (hexafluoroacetylacetonato)silver(I) (AgHFA), into dimethylacetamide solutions of poly(amic acid) prepared from 2,2‐bis(3,4‐dicarboxyphenyl)hexafluoropropane dianhydride and 2,2‐bis[4‐(4‐aminophenoxy)phenyl]hexafluoropropane. The thermal curing of solution‐cast silver(I)–poly(amic acid) films to 300°C led to cycloimidization of the amic acid with concomitant silver(I) reduction and the formation of a reflective, air‐side‐silvered surface at very low (2 wt % and 0.3 vol %) silver concentrations. The reflective surface evolved only when the cure temperature reached about 275°C, although X‐ray diffraction showed metallic silver in the hybrid film by 200°C. After a maximum specular reflectivity greater than 80% was achieved for the 2 wt % silver film, the specular reflectivity diminished sharply with further heating at a constant temperature of 300°C. Incorporating the AgHFA complex into the soluble, fully imidized form of poly{(1,3‐dihydro‐1,3‐dioxo‐2H‐isoindole‐2,5‐diyl)[2,2,2‐trifluoro‐1‐(trifluoromethyl)ethylidene](1,3‐dihydro‐1,3‐dioxo‐2H‐isoindole‐5,2‐diyl)‐1,4‐phenyleneoxy‐1,4‐phenylene[2,2,2‐trifluoro‐1‐(trifluoromethyl)ethylidene]‐1,4‐phenyleneoxy‐1,4‐phenylene} gave films that were 25% less reflective than those beginning with poly(amic acid). Though highly reflective, the films were not electrically conductive. The metalized membranes were thermally stable and maintained mechanical properties similar to those of the parent polyimide. Transmission electron microscopy revealed an air‐side, near‐surface layer of silver that was about 40 nm thick; the interior of the film had well‐dispersed metal particles with diameters mostly less than 2 nm. The near‐surface silver layer maintained its integrity because of physical entrapment of the metal nanoparticles beneath a thin layer of polyimide; that is, the practical adhesion of the metal layer was good. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2409–2418, 2007     

Polyimides derived from nonaromatic monomers: synthesis, characterization and potential applications

A number of mixed aromatic/cycloaliphatic as well as fully nonaromatic polyimides have been prepared. Whereas all the poly(amic acids) derived from nonaromatic diamines involved salt-formation during the initial stages of the polymerization, the majority of these eventually formed homogeneous, highly viscous polymer solutions. Only in a few select cases involving all nonaromatic monomers traditional solution polymerization was unsuccessful. The polyimide derived from hexafluoroisopropylidene diphthalic anhydride (6FDA) and trans- 1,4-diaminocyclohexane (DACH) yielded films with tough mechanical properties, a glass transition temperature of 360°C, good solvent resistance, and a low dielectric constant of 2.6. Thermal stability of this polyimide as determined by thermal gravimetric analysis in both air and nitrogen was quite good, exhibiting a weight loss of only 0.07 wt%/h at 350°C under isothermal conditions in nitrogen. However, mechanical properties as a function of thermal aging in both air and nitrogen indicated a maximum use temperature of only 350°C under inert conditions and less than 300°C in the presence of oxygen.     

High-performance polymer films. III. Preparation and characterization

A series of polyimide and copolyimide films were prepared by film casting, drying, and thermal imidization from the respective precursor poly(amic acid) (PAA) and copoly(amic acid) solutions derived from two dianhydrides, pyromellitic dianhydride (PMDA) and 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA), and two diamines, 4,4′-oxydianiline (ODA) and a proprietary aromatic diamine (PD) as monomers. Depending on the solution's inherent viscosity value (molecular weight) and the nature of the polymer chains (derived from rigid or flexible monomers), precursor poly(amic acid) and copoly(amic acid) solution concentrations of 8–12% (w/w) were found to be suitable for the preparation of good quality polyimide/copolyimide films. The recovery of film toughness and creasability from the brittleness at the intermediate temperature of the cure cycle depended not only on the molecular weight of the precursor poly(amic acids)/copoly(amic acids) but also on their chain flexibility. The poly(amic acid) derived from both rigid dianhydride and diamine practically gave rise to a brittle film of polyimide even after curing to 360°C. The resulting polyimide and copolyimide films were compared with Du Pont's Kapton H film. The density of the films was in the range 1.39–1.42 g/cm³. The thickness of most of the films was in the range 20–30 μm. The HPF 3 film, based on PMDA–PD, appeared to be highly colored (reddish brown), and the HPF 2 film, based on BTDA–ODA, had the lightest yellow coloring among the films in this investigation, including Kapton H film. HPF 2, HPF 6, and HPF 8 films were more amorphous than the other films. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 976–988, 2001     

Synthesis of poly(propylene glycol)‐grafted polyimide precursors and preparation of nanoporous polyimides

A novel approach to prepare a polyimide nanofoam was explored by using a polyimide precursor grafted with a labile poly(propylene glycol) (PPG) oligomer. The PPG‐grafted polyimide precursor, poly((amic acid)‐co‐(amic ester)), was synthesized via partial esterification of poly(amic acid) derived from pyromellitic dianhydride (PMDA) and 4,4′‐oxydianiline (ODA) with bromo‐terminated poly(propylene glycol) in the presence of K₂CO₃ in hexamethylphosphoramide and N‐methylpyrrolidone. The precursor polymer film was spin‐coated onto a glass substrate, then imidized at 200 °C under nitrogen, and subsequently the PPG graft was decomposed by heating the film at 300 °C for 9 h in air, resulting in the PMDA/ODA polyimide nanofoam. The precursor polymers, polyimides and foamed polyimides were characterized by a variety of techniques including ¹H‐NMR spectroscopy, Fourier‐transform infrared (FT‐IR) spectroscopy, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The homogeneously distributed nano‐sized pores of 20–40 nm were observed by transmission electron microscopy (TEM) of the foamed polyimide. Copyright © 2004 Society of Chemical Industry     

Beckmann rearrangement of cyclohexanone oxime to ε‐caprolactam in microreactors

Selectivities are presented of the Beckmann rearrangement of cyclohexanone oxime to ε‐caprolactam with oleum for various conditions in three microreactors, viz., Y‐junction, interdigital, and split and recombine mixers, followed by a 50‐cm long microchannel of 250 μm internal diameter. Cyclohexanone oxime is dissolved in cyclooctane, which is inert for oleum. The selectivity is measured in the temperature range of 80–132°C. The concentration range of caprolactam in the reaction mixture is 31–41 wt %, in oleum. The total volumetric flow rate is 0.4 ml/min, whereas the flow rate ratio of ε‐caprolactam/oleum over cyclohexanone oxime/cyclooctane ranges from 0.3 to 3. The selectivities measured with the three microreactors are: 70–99+%, 93–99+%, and 95–99+%, respectively. High ε‐caprolactam concentration (41 wt %), high temperature (110–132°C), and a ratio of free H₂SO₄ to SO₃ of unity have a negative effect on the selectivity. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Synthesis and properties of low‐color polyimide/silica hybrid films

A series of polyimide precursors, poly(amic acid)s, containing propyltrimethoxysliane at two chain ends were prepared from 4,4′‐bis(4‐amino‐2‐trifluoromethylphenoxy)biphenyl ( I ) with six commercially available dianhydrides, followed by end‐capping with 3‐aminopropyltrimethoxysilane (APrTMOS). A new class of fluorine‐containing polyimide/silica composite films ( III ) with chemical bonds between the fluorinated polyimide backbone and the silica network has been synthesized from the APrTMOS‐terminated precursors with tetramethoxysilane via the sol‐gel process and thermal cyclodehydration. The resultant hybrid films were light‐colored, flexible, and tough. They had high levels of thermal stability associated with high glass‐transition temperatures (>251°C), 10% weight‐loss temperatures in excess of 527°C, and char yields at 800°C in nitrogen higher than 60%. For a comparative study, the analogous nonfluorinated polyimide/silica hybrid films ( III′ ), based on 4,4′‐bis(4‐aminophenoxy)biphenyl ( I′ ), and the neat fluorinated polyimide films ( IV ), based on diamine I , were also synthesized and characterized. The hybrid films of the fluorinated series III showed a higher transparency and less color intensity when compared with the nonfluorinated III′ analogs. They also revealed a lower refraction index and birefringence than pure polyimides ( IV ). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 4046–4052, 2007     

Residual stress and thermal expansion of spun-on polyimide films

The residual stress in spin coated films and the effect of heat treatments on this stress were determined by the Fizeau interference method. Three types of spin coated polyimide (PI) films have been studied. Two of them were prepared by thermal conversion of their poly(amic acid)s (PAAs) and the third one by solvent evaporation of the soluble preimidized PI. For the imidized PI films the residual stress vs. bake temperature shows an inclined steplike behavior while this function for soluble PI is approximately linear. The room temperature stress relative to silicon substrates in fully baked films (400°C) is between 40 and 70 MPa and nearly independent of the film thickness. From the stress measurement, the thermal expansion coefficient and Young's moduli have also been obtained. The thermal expansion coefficient and the Young's modulus are in the order of 9.0 × 10^?6°C^?1 and 10 GPa, respectively. These values deviate from those published for bulk material which is explained by the in-plane orientation of the molecular chains in spun-on PI films.     

Preparation of Nanoporous Polyimide Films from Poly(urethane‐imide) by Thermal Treatment

Nanoporous polyimide films were prepared in two steps. The first step is the preparation of poly(urethane‐imide) films by casting blend solutions containing various weight percentages of poly(amic acid) and phenol blocked polyurethane prepolymer (from 1,6‐hexamethylene diisocyanate and poly(ethylene glycol)). Three poly(amic acid)s were obtained from biphenyltetracarboxylic dianhydride (or) 2,2‐bis(3,4‐dicarboxyphenyl)hexafluoropropane dianhydride with 1,4‐phenylenediamine (or) 2,5‐dimethyl‐1,4‐phenylenediamine. Poly(urethane‐imide) films were characterized by density and surface energy measurements, AFM, DSC, TMA, mechanical properties and TGA. In the second step, these films were thermally treated above 300 °C to give nanoporous polyimide films. During thermal treatment, less thermally stable urethane domains decomposed, leaving porous polyimide films. The presence of pores was confirmed by scanning electron microscopy (SEM). The dielectric constant of the polyimide film was found to decrease with increasing amounts of urethane content.

A nanoporous polyimide film.     

Preparation and characterization of polyethylene oxide (PEO)/gelatin blend for biomedical application: Effect of gamma radiation

polyethylene oxide (PEO)/gelatin blend membranes of four different compositions (w/w) (5/95, 10/90, 20/80, and 30/70) were prepared by solution casting. The films were irradiated by gamma radiation at a total dose of 250 krad (dose rate of 321 krad/h). The X‐ray diffractograms demonstrate both the PEO and radiation influences on the blend thus enhancing crystallinity of gelatin. X‐ray diffractograms of irradiated blend films containing 30% PEO showed highest integrated intensity. The DTA and TGA study showed that the irradiated blend films are more thermally stable than the non‐irradiated films. TMA study showed that the incorporation of PEO into gelatin increased melting point of the blend films. The melting point for irradiated gelatin film changes from 52.9°C to 75.6°C and the glass point changes from 60.3°C to 90.6°C. The phase separation and compatibility of the PEO/gelatin blend films were studied by scanning electron microscopy (SEM). The experimental results showed that the blend films exhibit higher thermal stability and improved mechanical properties in dry state, which suggests the occurrence of interaction detected by XRD and DTA among gelatin, PEO, and water molecules in the films. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Thermal and electrical behaviour of some hybrid polyimide films containing barium and titanium oxides

Aromatic polyimides are high‐performance polymers used in applications demanding service at enhanced temperature while maintaining their structural integrity and excellent combination of chemical, physical and mechanical properties. The incorporation of various metallic additives into a polyimide matrix improves its properties, leading to materials required by specific applications. Hybrid polyimide films containing barium and titanium oxides having thicknesses in the range of tens of micrometres were prepared. These films were obtained using the sol–gel technique starting from a poly(amic acid) and a soluble precursor of metal oxides. They exhibited good thermal stability having an initial decomposition temperature above 460 °C, and a glass transition temperature in the range 217–238 °C. Two subglass transitions, γ and β, were evident from dynamic mechanical analysis and dielectric spectroscopy. A study of the thermal and electrical behaviour of some hybrid polyimide films containing barium and titanium oxides is presented. On increasing the concentration of metal oxides, an increase of dielectric constant and a decrease of thermal stability of the hybrid films were observed. The presence of metal oxides shifted the glass transition temperature and the temperature of the β transition to higher values. Copyright © 2009 Society of Chemical Industry     

Synthesis and characterization of a positive‐working,aqueous‐base‐developable photosensitive polyimide precursor

A positive‐working, aqueous‐base‐developable photosensitive polyimide precursor based on poly(amic ester)‐bearing phenolic hydroxyl groups and a diazonaphthoquinone photosensitive compound was developed. The poly(amic ester) was prepared from a direct polymerization of 2,2′‐bis‐(3‐amino‐4‐hydroxyphenyl)hexafluoropropane and bis(n‐butyl)ester of pyromellitic acid in the presence of phenylphosphonic dichloride as an activator. Subsequently, the thermal imidization of the poly(amic ester) precursor at 300°C produced the corresponding polyimide. The inherent viscosity of the precursor polymer was 0.23 dL/g. The cyclized polyimide showed a glass‐transition temperature at 356°C and a 5% weight loss at 474°C in nitrogen. The structures of the precursor polymer and the fully cyclized polymer were characterized by Fourier transform infrared spectroscopy and ¹H‐NMR. The photosensitive polyimide precursor containing 25 wt % diazonaphthoquinone photoactive compound showed a sensitivity of 150 mJ/cm² and a contrast of 1.65 in a 3 μm film with 1.25 wt % tetramethylammonium hydroxide developer. A pattern with a resolution of 10 μm was obtained from this composition. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 352–358, 2002     

Thermal and electrical behavior of polyimide/silica hybrid thin films

Silica‐containing polyimide films were prepared by sol‐gel technique using a poly(amic acid) and tetraethoxysilane. The poly(amic acid) was synthesized by solution polycondensation reaction of 4,4′‐oxydiphthalic anhydride with 2,6‐bis(3‐aminophenoxy)benzene and an aminosilane coupling agent, 3‐aminopropyltriethoxysilane. The properties of these films, such as water vapors sorption capacity, dynamic contact angles and contact angle hysteresis, thermal, and electrical behavior have been evaluated with respect to their structure. The polymer films exhibited good thermal stability having the initial decomposition temperature above 450°C, glass transition temperature in the range of 223?228°C, and low‐dielectric constant in the range of 2.64?3.16. Two subglass transitions, γ and β, were evidenced by dynamic mechanical analysis and dielectric spectroscopy. The surface morphology and the roughness were investigated by atomic force microscopy and scanning electron microscopy. POLYM. ENG. SCI., 2010. © 2009 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     

Water‐sorption behavior of P‐phenylene diamine–based polyimide thin films

Four different p‐PDA–based polyimide thin films were prepared from their respective poly(amic acid)s through thermal imidization at 400°C: poly(p‐phenylene pyromellitimide) (PMDA‐PDA); poly(p‐phenylene biphenyltetra carboximide) (BPDA‐PDA); poly(p‐phenylene 3,3′,4,4′‐oxydiphthalimide) (ODPA‐PDA); and poly(p‐phenylene 4,4′‐hexafluoroisopropylidene diphthalimide) (6FDA‐PDA). Water‐sorption behaviors of polyimide films were gravimetrically investigated at 25°C and 22–100% relative humidity by using the modified electromicrobalance (Thin Film Diffusion Analyzer). The diffusion coefficients of water for the polyimides varies in the range of 1.6 to 10.5 × 10⁻¹⁰ cm²/s, and are in the increasing order: BPDA‐PDA < PMDA‐PDA ∼ ODPA‐PDA < 6FDA‐PDA. The water uptakes of polyimides vary from 1.46 to 5.80 wt %, and are in the increasing order: BPDA‐PDA < ODPA‐PDA < 6FDA‐PDA < PMDA‐PDA. The water‐sorption behaviors for the p‐PDA–based polyimides are closely related to the morphological structure; specifically, the diffusion coefficients in p‐PDA–based polyimide thin films are closely related to the in‐plane orientation and mean intermolecular distance, whereas the water uptakes are affected by the packing order. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1315–1323, 2000     

Polyimide molecular composites containing a stiff‐chain polymer derived from 1,5‐diaminonaphathalene and pyromellitic dianhydride

Polyimide molecular composite (MC) films were prepared by embedding a stiff‐chain polyimide (PI_S) in the ductile matrix of a flexible‐chain polyimide (PI_F) by blending their respective poly(amic acid) precursor solutions, followed by casting, drying, and thermal imidization upto 300°C. The PI_S was prepared from pyromellitic dianhydride (PMDA) and 1,5‐diaminonaphathalene (DAN), whereas the PI_F was prepared from the same dianhydride and 4,4′‐oxydianiline (ODA). Transparent, tough, and creasable MC films were obtained with 2.5–40 wt% of PI_S content. The disruption of crystalline order of PI_S in the MC films evidenced its fine dispersion in the matrix. Visco‐elastic measurements showed a single and enhanced value of the glass transition temperature for MC films indicating miscibility of this polyimide pair. Furthermore, the variation of charge transfer (CT) fluorescence intensity with the PI_S content in the blends verified complete miscibility upto 30 wt% of PI_S loading. These MCs showed a notable enhancement in the mechanical properties. Among all, the blend containing 30 wt% of stiff‐chain molecules gave the best combination of properties when compared with the matrix polyimide: a 50% higher value of tensile modulus, a 17°C rise in the glass transition temperature, and better thermal stability. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

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     

Enhanced crystallization of poly(lactide) stereocomplex by xylan propionate

The effect of xylan propionate (XylPr) as a novel biomass‐derived nucleating agent on the poly(lactide) sterecomplex was investigated. Addition of XylPr to an enantiomeric blend of poly(l ‐lactide) (PLLA) and poly(d ‐lactide) (PDLA) was performed in either the solution state or molten state. The solution blend of PLLA/PDLA with XylPr was prepared by mixing equal volumes of 1 wt% XylPr/PLLA and 1 wt% XylPr/PDLA solutions in chloroform and precipitating in methanol. The solution blend with XylPr showed shorter half‐time crystallization than the solution blend without XylPr in isothermal crystallization between 80 and 140 °C, although homocrystallization occurred. Enhanced stereocomplex crystallization in the solution blend with XylPr was observed at 180 °C, where no crystallization occurred in the solution blend without XylPr. Addition of XylPr to PLLA/PDLA blend in the molten state was performed at 240 °C. Thereafter, the melt blend of PLLA/PDLA with or without XylPr was either quenched in iced water or isothermally crystallized directly from the melt. Isothermal crystallization of the melt‐quenched blend with XylPr gave a similar result to the solution blend with XylPr. In contrast, the melt‐crystallized blend with XylPr formed only stereocomplex crystals after crystallization above 140 °C. Furthermore, the melt‐crystallized blend with XylPr showed a higher crystallinity index and melting temperature than the melt‐crystallized blend without XylPr. This shows that XylPr promotes stereocomplex crystallization only when the blend of PLLA/PDLA with XylPr is directly crystallized from the molten state just after blending. © 2016 Society of Chemical Industry     

Polyimide Ultrafiltration Membranes with High Thermal Stability and Chemical Durability

Abstract

Asymmetric ultrafiltration membranes based on poly[(4,4′-oxydiphenylene)pyromelliteimide] were produced by wet technique from prepolymer casting solution, followed by solid-phase conversion of the prepolymer membranes into polyimide insoluble form at 200°C. It was demonstrated that by adding benzimidazole to the casting solution and filling of prepolymer membrane pores with inert high-boiling oil prior to thermal treatment allow us to prepare asymmetric porous polyimide membranes. The main characteristics of the membranes obtained (permeability coefficients and molecular weight cut-off) match those typical to ultrafiltration membranes. It was found that the developed asymmetric ultrafiltration polyimide membranes have excellent thermal and chemical resistance. The membranes retain rigidity above Tg (360°C) and are chemically stable at temperatures up to 400°C. The developed membranes are resistant against swelling and dissolving in aggressive and organic media including amide solvents.     

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