Processable aromatic polyimides

Two similar polyimide systems were synthesized and characterized. The only structural difference was a sulfide linkage in the anhydride-derived portion of the first system vs. a sulfone linkage in the second. Their physical, mechanical, melt-flow and thermal properties, and their resistance to some of the more common solvents were determined. The flow properties of these polyimides indicate a potential for melt processability.     

Preparation and fabrication of aromatic polyimides

Aromatic polyimides were prepared from pyromellitic dianhydride and a number of aromatic diamines. The effect of certain variables on the polymerization to, and the degradation of, the intermediate polypyromellitamic acids was studied, and a previously unrecorded reaction intermediate was isolated and identified. From these studies the conditions necessary to obtain high molecular weights were defined. Techniques were developed for the fabrication of satisfactory films and moldings.     

Miscible blends of polybenzimidazole and polyaramides with polyvinylpyrrolidone

The blend behavior of polybenzimidazole and a series of polyaramides with polyvinylpyrrolidone is presented. Regardless of their chemical structure, all systems showed miscible blends over the composition range investigated. This may offer the opportunity to extend the application range of these basically structural materials into the area of functional polymers. Especially in membranes, the addition of the highly hydrophilic polyvinylpyrrolidone leads to a considerable increase in performance, i.e., in flux and antifouling behavior. © 1994 John Wiley & Sons, Inc.     

Miscible chitosan/tertiary amide polymer blends

The miscibility of five chitosan/tertiary amide polymer blend systems was studied. Based on the optical transparency of the blend and the existence of a single glass transition temperature, chitosan was found to be miscible with poly(N‐vinyl‐2‐pyrrolidone), poly(N‐methyl‐N‐vinylacetamide), poly(N,N‐dimethylacrylamide), poly(2‐methyl‐2‐oxazoline), and poly(2‐ethyl‐2‐oxazoline). Fourier transform infrared spectroscopy showed the existence of hydrogen‐bonding interactions between chitosan and the tertiary amide polymers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1785–1790, 2000     

High-temperature reactive thermoplastic aromatic polyimides

A series of high molecular weight aromatic enyne polyimides were prepared by the condensation of various aromatic dianhydrides with (E)-1,3-bis(3-aminophenyl)-1-buten-3-yne. The polymers were soluble in common organic solvents and exhibited intrinsic viscosities as high as 0.43 (in DMAC at 30°C) with glass transition temperatures ranging from 200 to 265°C. The new thermoplastic materials have the capability to become lightly crosslinked when thermally treated during a stimulated high-temperature thermoforming process. Thermal treatment diminishes the various solvent-induced problems inherent in linear polymeric materials and advances the glass transition temperature. Copolymers were also prepared using 1,3-bis(3-aminophenoxy)benzene and (E)-1,3-bis(3-aminophenyl)-1-buten-3-yne in an effort to obtain various percentages of enyne along the polymer backbone and, therefore, control the degree of crosslinking. The solvent resistance of selected copolymer compositions both in neat resin and thermoplastic composite form was evaluated.     

Synthesis and characterization of some aromatic polyimides

The diamine 2‐methyl‐1,3‐bis(4‐aminophenyloxy)benzene was prepared via a nucleophilic substitution reaction and was characterized with Fourier transform infrared, elemental analysis, and ¹H‐ and ¹³C‐NMR spectroscopy. The prepared diamine was also characterized with single‐crystal analysis. The geometric parameters of C₁₉H₁₈N₂O₂ were in the usual ranges. The dihedral angles between the central phenyl ring and the two terminal aromatic rings were 88.9 and 91.6°. The crystal structure was stabilized by N? H···N hydrogen bonds. The diamine was then polymerized with 3,3′,4,4′‐benzophenone tetracarboxylic acid dianhydride, 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride, 3,4,9,10‐perylenetetracarboxylic acid dianhydride, and pyromellitic dianhydride by either a one‐step solution polymerization reaction or a two‐step procedure. These polymers had inherent viscosities ranging from 0.61 to 0.85 dL/gm. Some of the polymers were soluble in most common organic solvents even at room temperature, and some were soluble on heating. The degradation temperatures of the resultant polymers fell in the range of 260–500°C in nitrogen (with only 10% weight loss). The specific heat capacity at 200°C ranged from 1.0 to 2.21 J g^?1 K^?1. The temperatures at which the maximum degradation of the polymer occurred ranged from 510 to 610°C. The glass‐transition temperatures of the polyimides ranged from 182 to 191°C. The activation energy and enthalpy of the polyimides ranged from 44.44 to 73.91 kJ/mol and from 42.58 to 72.08 kJ/mol K, respectively. The moisture absorption was found in the range of 0.23–0.71%. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Miscible blends of conductive polyaniline with tertiary amide polymers

Polyaniline (PANI) was doped with p-phenolsulfonic acid (PSA) or 5-sulfosalicylic acid (SSA). The PANI salts were blended with poly(N-vinyl-2-pyrrolidone), poly(N-methyl-N-vinylacetamide), poly(N,N-dimethylacrylamide), or poly(2-methyl-2-oxazoline) by solution casting from dimethyl sulfoxide. Blends containing up to 50% by weight of PANI salt were homogeneous and each exhibited a single glass transition temperature, indicating miscibility. Fourier transform infrared spectroscopic studies indicated that the carbonyl groups of the tertiary amide polymers interacted with the PANI salt as evidenced by the development of a shoulder at a lower frequency in the carbonyl stretching band. Electrical conductivities of the blends are in the range 10⁻⁵ to 10⁻³ S/cm, depending on the blend composition. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1839–1844, 1998     

Gas-separation applications of miscible blends of isomeric polyimides

Blends of polyimide isomers containing hexafluoroisopropylidene in the central moiety of the diamine residue have been studied. The isomers differed by having either a meta or a para linkage between the diamine and dianhydride residues. The miscibility of these materials was investigated by studying the glass transition temperature behavior using differential scanning calorimetry. Mixtures of isomer pairs, such as 6FDA–6FmDA and 6FDA–6FpDA, exhibited one glass transition temperature. T_g, and were therefore miscible. Mixtures of nonisomer pairs exhibited two T_g's and were immiscible. The gas sorption and transport properties of the blends of the 6FDA–6FmDA and 6FDA–6FpDA isomers were characterized for a variety of gases at 35°C for pressures up to 60 atm. The permeabilities and permselectivities in the miscible blends fell between those of the pure components and were approximately logarithmic averages of the pure component properties. The miscibility of the polyimide isomers enables one to tailor the composition of the material to optimize the gas separation and mechanical properties. © 1993 John Wiley & Sons, Inc.     

Gas permeation properties of hexafluoro aromatic polyimides

Two hexafluoro-substituted aromatic polyimides, 6FDA-p-PDA and 6FDA-4,4′-ODA, were synthesized. The influence of some synthetic conditions on physical properties and gas permeabilities of the 6FDA polyimide membranes were studied. Gas permeabilities and permselectivities of six different gases for the homogeneous films have been determined at 15–35°C and at pressures up to 10 atm. 6FDA polyimide composite membranes with asymmetric structure were prepared by the solution-casting method. The membranes showed exceptionally high permeation fluxes and permselectivities. No capability deterioration of asymmetric membrane was observed during 19 days operation with pure gases. © 1993 John Wiley & Sons, Inc.     

Thermal expansion behavior of various aromatic polyimides

The thermal expansion behavior for various aromatic polymides was investigated. Usally polymers, including polyimides, have high thermal expansion coefficients (3–6 × 10^?5 K^?1), compared with metals and ceramics. However, there are some polyimides which have very low thermal expansion coefficients below 1 × 10^?5 K^?1. This property was observed for the polymides obtained from pyromellitic dianhydride or 3,3′ 4,4′-biphenyltetracarboxylic dianhydride and aromatic diamines which were constituted of only benzene rings fused at para positions. It was proposed that their low thermal expansion coefficient related to the linearity in their polymer molecular skeltons.     

Preparation and characterization of aromatic polyimides and related copolymers

Copolyimides containing BTDA-3DDS and BTDA-4ODA units have been synthesized by solution imidization methods. The copolyimides have high T_g's (267–283°C) and high decomposition temperatures (540–575°C; nitrogen); both properties are dependent on composition. Those copolymides with low concentrations of BTDA-4ODA are generally soluble in organic solvents, whereas those copolyimides with higher BTDA-4ODA content are only partially soluble or insoluble. However, all the copolyimides prepared can be compression molded. It has also been found that segmental motion above T_g is heavily suppressed in the BTDA-4ODA homopolymer relative to that in the BTDA-3DDS homopolymer. This reduction in molecular motion may severely hinder the solubility and fusibility of the BTDA-4ODA homopolymer. © 1993 John Wiley & Sons, Inc.     

Miscible polymer blends containing poly(vinyl chloride)

Polymer blends have received particular interest in the past several decades in both industrial and academic research. An initial survey of miscible polymer pairs (1) (1968) revealed 12 combinations. A later survey (2) (1979) noted approximately 180 miscible pairs. Today possibly over 500 miscible combinations have been noted in the open and patent literature (3). However, the vast majority of possible polymer blend combinations are not miscible (thus phase separated). A significant number of diverse polymer structures have been shown to exhibit miscibility with PVC. Several of these blends have been studied in detail and have shown specific interactions primarily involving the α-hydrogen and PVC (considered the proton donor in proton donor-proton acceptor hydrogen bonding type interactions). The blend of poly(?-caprolactone) with PVC illustrates this interaction and has been reported in many published papers. While polymer miscibility in PVC blends offers significant academic interest, industrial utility is also of considerable importance. The addition of low T_g, miscible polymers to PVC offers permanent plasticization. The addition of high T_g, miscible polymers to PVC yields the desired heat distortion temperature enhancement of rigid PVC. A specific example of permanent plasticization involves nitrile rubber blends which have been commercial since the early 1940's. This presentation will review the growing number of polymers noted to be miscible with PVC. The importance of specific interactions will be discussed.     

Miscibility studies in blends of polybenzimidazoles and poly(4-vinyl pyridine)

Poly[2,2'-(m-phenylene)-5,5'-bibenzimidazole] (PBI) is shown to be miscible with poly(4-vinyl pyridine) over the entire composition range. Experiments were performed with commercial PBI as well as a lower molecular weight material synthesized by us. Blend miscibility is evidenced by single glass transition temperature intermediate between the pure polymers. Hydrogen bonding between the components was detected by infrared spectroscopy.     

Synthesis and properties of aromatic polyimides based on ether-sulfone-diamines

Two diamine monomers, 4,4′-[sulfonylbis(1,4-phenyleneoxy)]dianiline (III _a ) and 4,4′-[sulfonylbis(2,6-dimethyl-l,4-phenyleneoxy)]dianiline (III _b ), were prepared by an aromatic nucleophilic substitution of 4,4′-sulfonyldiphenol (I _a ) and 4,4′-sulfonylbis(2,6-dimethylphenol) (I _b ) with p-chloronitrobenzene in the presence of potassium carbonate, followed by hydrazine catalytic reduction of the intermediate dinitro compounds. The diamines III _a and III _b were used as monomers with various aromatic tetracarboxylic dianhydrides (IV _a–f ) to synthesize polyimides. The polymerization was conducted in two steps via the formation of a poly(amic acid) precursor followed by thermal cyclodehydration. The poly(amic acid)s had inherent viscosities above 0.87 and up to 2.56 dL/g. Most poly(amic acid)s could be coated and thermodehydrated into flexible and transparent polyimide films. The polyimides derived from the dianhydrides containing-O-and-SO₂-or-C(CF₃)₂-bridging groups between the phthalic anhydride units were soluble in some organic solvents such as N,N-dimethylacetamide (DMAc) and N,N-dimethylformamide (DMF). The glass transition temperatures (T_g) of the polyimides were in the range from 254 to 300 °C. The methyl-substituted polyimides exhibited slightly higher solubility and higher T_g compared to the corresponding unsubstituted polyimides. Thermogravimetric analysis (TG) showed that the polyimides containing methyl substitutents started to lose weight around 450 °C and the unsubstituted ones started to lose weight around 550 °C.     

Comparative study of aromatic polyimides containing methylene units

Two series of aromatic polyimides have been synthesized by solution polycondensation of certain aromatic dianhydrides with two aromatic diamines containing methylene groups; one of the diamines has also a methyl substituent on each benzene ring. These polymers have been studied with regard to their solubility, thermal stability, film forming ability, and mechanical properties of their films.     

Dynamic relaxation characteristics of thermally rearranged aromatic polyimides

The glass–rubber and sub-glass relaxation characteristics of ortho-functionalized aromatic polyimides and thermally rearranged polymers were investigated by dynamic mechanical and dielectric methods. Soluble polyimides (HAB–6FDA; APAF–ODPA) were synthesized by chemical and thermal imidization and subject to thermal rearrangement at elevated temperature. For the thermal exposure histories investigated, mass loss studies indicated partial conversion of the polyimide precursor, suggesting the formation of TR copolymers containing both benzoxazole units and residual imide segments. Measurement of storage modulus and loss tangent was used to follow the thermal rearrangement process in-situ as reflected in the suppression of the polyimide glass transition as a function of precursor structure, the nature of the ortho functional groups and prior thermal exposure. In addition, changes in the position and intensity of local relaxations detected across the sub-glass temperature range were correlated with the degree of thermal rearrangement in these polymers.     

Miscible blends of poly(aryl ether ketone)s and polyetherimides

A new class of high performance engineering resins, poly(aryl ether ketone)s, has emerged with a property balance not offered by existing polymeric materials. Blends of poly(aryl ether ketone)s with other polymers have not been described in the open literature, although several patents have revealed interesting and important properties of certain blend combinations. Ultem polyetherimide has been found to be miscible over the entire composition range and as a consequence is a very effective heat distortion temperature builder, particularly if the poly(aryl ether ketone) is allowed to crystallize. Crystallization kinetics and mechanical properties were studied as a function of blend composition and poly(aryl ether ketone) melting point. The blends exhibited a maximum in toughness at intermediate compositions along with an accompanying maximum in poly(aryl ether ketone) crystallinity. The chemical resistance of the polyetherimide is significantly improved with the addition of a poly(aryl ether ketone). In organic chemicals, the improvement was expected when tensile stress was plotted vs. log time to rupture. However, in aqueous bases, the resistance of the blends was much greater than anticipated. This property profile suggests that these blends will be useful as thermoplastic composite matrix resins.     

Miscible raw lignin/nylon 6 blends: Thermal and mechanical performances

Environmentally friendly bio‐filled composites of various proportions of polyamide 6 (PA6) and technical lignin have been prepared using a twin‐screw extruder. Transmission electron microscopy has been used to investigate the morphology of the composites. It reveals homogeneous single phase system, indicating the miscibility of PA6 and lignin. The glass transition temperature of the blends, determined by DMA, was shifted systematically to higher temperature with increasing concentration of lignin which highlights the miscibility of both components. In addition, Fourier Transform Infrared analyses have shown that new specific hydrogen‐bonding interactions are formed between hydroxyl groups of lignin and amine groups of the PA6. The presence of these intermolecular interactions between PA6 and lignin strongly influenced the thermal stability of the blends by lowering the onset of the blend's degradation process. However, the blends exhibit good mechanical properties whatever the lignin content. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42963.     

Preparation and characterization of metal‐containing aromatic polyimides

A series of novel metal‐containing aromatic polyimides were synthesized from divalent metal oxide/hydroxide (MO/M(OH)₂) (M = Ba, Sr, Ca, Mg, Zn, Cd, Co, Ni, Pb, Cu), p‐aniline sulfonic acid (ASA), and 3,3′‐4,4′‐benzophenonetetracarboxylic dianhydride (BTDA). The C, H, N, and S contents were determined by elemental analysis, their structures were characterized by proton nuclear magnetic resonance (¹H‐NMR) and Fourier transform infrared (FT‐IR) spectroscopy, and the thermal properties of the polymers were also studied by TG–DTA. It is found that metal‐containing polyimides have a higher thermal stability. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2363–2369, 2000