Synthesis and characterization of novel aromatic polyimides from 4,4‐bis(p‐aminophenoxymethyl)‐ 1‐cyclohexene

A novel diamine, 4,4‐bis(p‐aminophenoxymethyl)‐1‐cyclohexene (CHEDA), was synthesized from 4,4‐bis(hydroxymethyl)‐1‐cyclohexene and p‐chloronitrobenzene by nucleophilic aromatic substitution and subsequent catalytic reduction of the intermediate dinitro compound. A series of aromatic polyimides were prepared from CHEDA and commercial dianhydrides with varying flexibility and electronic character in two‐step direct polycondensation reactions. High molecular weight polyimides with intrinsic viscosities between 0.57 and 10.2 dL/g were obtained. Most of these polyimides, excluding those from PMDA and BPDA, were soluble in polar aprotic solvents such as NMP and DMAc, and many were also soluble in CHCl₃ and THF. DSC analysis revealed glass transitions in the range of 190 to 250°C. No significant weight losses occurred below 450°C in nitrogen and 350°C in air. Bromination and epoxidation of cyclohexene double bond in CHDEA–6FDA (3e) were investigated as examples of possible polymer modifications. Qualitative epoxidation and selective bromination of the double bond were demonstated. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1189–1197, 1999     

Physical aging of an amorphous polyimide: Enthalpy relaxation and mechanical property changes

The physical aging behavior of an isotropic amorphous polyimide possessing a glass transition temperature of approximately 239°C was investigated for aging temperatures ranging from 174 to 224°C. Enthalpy recovery was evaluated as a function of aging time following sub‐T_g annealing in order to assess enthalpy relaxation rates, and time‐aging time superposition was employed in order to quantify mechanical aging rates from creep compliance measurements. With the exception of aging rates obtained for aging temperatures close to T_g, the enthalpy relaxation rates exhibited a significant decline with decreasing aging temperature while the creep compliance aging rates remained relatively unchanged with respect to aging temperature. Evidence suggests distinctly different relaxation time responses for enthalpy relaxation and mechanical creep changes during aging. The frequency dependence of dynamic mechanical response was probed as a function of time during isothermal aging, and failure of time‐aging time superposition was evident from the resulting data. Compared to the creep compliance testing, the dynamic mechanical analysis probed the shorter time portion of the relaxation response which involved the additional contribution of a secondary relaxation, thus leading to failure of superposition. Room temperature stress‐strain behavior was also monitored after aging at 204°C, with the result that no discernible embrittlement due to physical aging was detected despite aging‐induced increases in yield stress and modulus. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1931–1946, 1999     

Suppression of CO2-plasticization by semiinterpenetrating polymer network formation

CO₂-induced plasticization may significantly spoil the membrane performance in high-pressure CO₂/CH₄ separations. The polymer matrix swells upon sorption of CO₂, which accelerates the permeation of CH₄. The polymer membrane looses its selectivity. To make membranes attractive for, for example, natural gas upgrading, plasticization should be minimized. In this article we study a polymer membrane stabilization by a semiinterpenetrating polymer network (s-ipn) formation. For this purpose, the polyimide Matrimid 5218 is blended with the oligomer Thermid FA-700 and subsequently heat treated at 265°C. Homogeneous films are prepared with different Matrimid/Thermid ratios and different curing times. The stability of the modified membrane is tested with permeation experiments with pure CO₂ as well as CO₂/CH₄ gas mixtures. The original membrane shows a minimum in its permeability vs. pressure curves, but the modified membranes do not indicating suppressed plasticization. Membrane performances for CO₂/CH₄ gas mixtures showed that the plasticizing effect indeed accelerates the permeation of methane. The modified membrane clearly shows suppression of the undesired methane acceleration. It was also found that just blending Matrimid and Thermid was not sufficient to suppress plasticization. The subsequent heat treatment that results in the s-ipn was necessary to obtain a stabilized permeability. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1547–1556, 1998     

Interfacial phenomena in polymer films and generation of maxwell displacement current

Interfacial electrostatic phenomena in ultrathin polyimide films have been examined, and the space charge distribution and electronic density of states have been determined. The presence of excess negative charges at the film-metal interface of nanometer thickness has been revealed and the alignment of the surface Fermi level of polymer films and Fermi level of metals have been elucidated. Taking into account the interfacial space charge, a step structure observed in the I-V characteristic of metal-polyimide-rhodamine-polyimide-metal junction, very similar to Coulomb staircase, is well explained. Furthermore, the electrical breakdown mechanism of a nanometer-thick polyimide film is found quite different from that of micrometer-thick films, owing to the presence of this interfacial nanometric space charge. Finally, for a profound understanding of the behaviour of surface monolayer, the Maxwell displacement current measurement coupled with optical second harmonic generation measurement has been employed.     

Novel method for the preparation of poly(urethane–imide)s and their properties

A polymer blend consisting of polyimide (PI) and polyurethane (PU) was prepared by means of a novel approach. PU prepolymer was prepared by the reaction of polyester polyol and 2,4-tolylenediisocyanate (2,4-TDI) and then end-capped with phenol. Poly(amide acid) was prepared from pyromellitic dianhydride (PMDA) and oxydianiline (ODA). A series of oligo(amide acid)s were also prepared by controlling the molar ratio of PMDA and ODA. The PU prepolymer and poly(amide acid) or oligo(amide acid) solution were blended at room temperature in various weight ratios. The cast films were obtained from the blend solution and treated at various temperatures. With the increase of polyurethane component, the films changed from plastic to brittle and then to elastic. The poly(urethane–imide) elastomers showed excellent mechanical properties and moderate thermal stability. The elongation of films with elasticity was more than 300%. The elongation set after the breaking of films was small. From the dynamic mechanical analysis, all the samples showed a glass transition temperature (T_g) at ca. −15°C, corresponding to T_g of the urethane component, suggesting that phase separation occurred between the two polymer components, irrespective of polyimide content. TGA and DSC studies indicated that the thermal degradation of poly(urethane–imide) was in the temperature range 250–270°C. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3745–3753, 1997     

Transmission electron microscopy of 3F/PMDA-polypropylene oxide triblock copolymer based nanofoams

Transmission electron microscopy was performed on a polymeric nanofoam material, derived from a triblock copolymer composed of a fluorinated polyimide center block, 3F/PMDA (derived from pyromelletic dianhydride (PMDA) and 1,1-bis(4-aminophenyl)-1-phenyl-2,2,2-trifluoroethane (3F)) and polypropylene oxide (PO) end blocks. The cast and imidized polymer exhibits a microphase-separated morphology consisting of PO microdomains within a polyimide matrix. The final nanofoam material is obtained by decomposing PO microdomains into low molecular weight products, which diffuse out of the polyimide matrix leaving nanometer length scale voids. Ruthenium tetroxide staining prior to microscopy was used to enhance the contrast between the 3F/PMDA matrix and the PO microdomains or voids, which permitted a more detailed view of the microstructure of both the foamed and unfoamed materials. From the power spectra of the micrographs, spatial correlation between the PO microdomains in the unfoamed material and between the voids in the foam were found. An interdomain separation distance of ca. 37 nm was observed. Analysis of the image yielded an average area of 411 nm² for the PO domains. The analysis indicated that the PO domains were oblong, having average major and minor dimensions of 35 and 12.5 nm, respectively. An autocorrelation of the image showed that the domain center of masses were positioned 41 nm apart, in close agreement with the domain spacing (ca. 37 nm) found as described above. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1067–1076, 1997     

Effect of ultraviolet light irradiation on gas permeability in polyimide membranes. 1. Irradiation with low pressure mercury lamp on photosensitive and nonphotosensitive membranes

Two types of polyimide membranes; one crosslinkable and the other noncrosslinkable using ultraviolet light irradiation (UV irradiation), were prepared and investigated concerning the effect of UV irradiation on their gas permeabilities and selectivities. Permeability and diffusion coefficients for O₂, N₂, H₂, and CO₂ were determined using the vacuum pressure and time lag method. Sorption properties for carbon dioxide were carried out to evaluate the changes in the free volume in the membranes due to the irradiation. In both membranes, permeability coefficients for all gases used in this study decreased and permselectivity, particularly for H₂ over N₂, increased with increasing UV irradiation time without a significant decrease in the flux of H₂. The coefficients depended on the membrane thickness, suggesting asymmetrical changes in both membranes due to UV irradiation. It was suggested by an attenuated total reflection (ATR) FTIR method and analysis of the gas sorption properties of the membranes that the physical changes due to UV irradiation at the irradiated side in both membranes significantly affected their gas permeation properties compared with the chemical changes, especially the crosslinking in the crosslinkable type. © 1997 John Wiley & Sons, Inc. J. Polym Sci B: Polym Phys 35: 2259–2269, 1997     

Covalently Linked,Transparent Silica–Poly(imide) Hybrids

Silica–poly(imide) hybrid materials have been developed which rely on interactions between the organic and inorganic phases to improve homogeneity. Using this method, transparent hybrids have been formed over all compositions studied. The hybrids show improved hardness and modulus with increasing silica content. Links between the two phases result in very finely divided microstructures. Hybrids such as these might be very important as barrier layers or scratch-resistant coatings. © 1997 John Wiley & Sons, Ltd.     

Synthesis of a hexafluoropropylidene-bis(phthalic anhydride)-based polyimide and its conducting polymer composites with polypyrrole

A new electrically conducting composite film from polypyrrole and 4,4′-(hexafluoroisopropylidene)-bis(phthalic anhydride)-based polyimide was prepared. Pyrrole and the dopant ion can easily penetrate through the polyimide substrate and electropolymerize on the platinum (Pt) electrode due to the swelling of the polyimide on the metal electrode. The electrochemical properties of polypyrrole-polyimide (PPy/PI) composite films have been investigated by using cyclic voltammetry. The PPy/PI composite film is suitable for use as the electroactive material owing to its stable and controllable electrochemical properties. The electrical conductivity of composites falls in the range 0.0035–15 S/cm. Scanning electron micrograph, FTIR, and thermal studies indicate that PPy and PI form a homogeneous material rather than a simple mixture. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 3009–3016, 1997