Synthesis and Characterization of Wholly Aromatic Semicrystalline Polyimides Based Upon Bis(4-Aminophenoxy) Benzenes

Semicrystalline thermoplastic polyimides based upon bis(4-aminophenoxy)benzene and related "triphenyl ether" diamines were synthesized via the classical two step amic acid route. More specifically, polyimides were derived from para linked 1,4-bis(4-aminophenoxy)benzene, or TPEQ (triphenyl ether diamine- hydroquinone) and its meta isomer 1,3-bis(4-aminophenoxy)benzene, or TPER (triphenyl ether diamine-resorcinol). The reaction of these diamines with rigid or semi-rigid dianhydrides such as pyromellitic dianhydride (PMDA), biphenyl dianhydride (BPDA), and oxydiphthalic anhydride (ODPA) yields very thermally stable semi-crystalline polymers which have excellent resistance to organic liquids. Amorphous polyimides could be derived from hexafluoroisopropylidene-linked diphthalic anhydride (6FDA), but these systems were not extensively investigated. Importantly, molecular weight characterization of the semicrystalline systems at the soluble amic acid stage was successful by employing hydrodynamic volume calibrated, viscosity detector size exclusion chromatography (SEC). The experimental values were found to be within the targeted <M_n> range of 20-30,000 g/mole. Polyimide powders derived from these ether diamines were prepared by solution imidization at 180°C, to afford about 70% imidized structures as judged by dynamic thermal gravimetric analysis (TGA), before crystallization/precipitation occurred. Relatively small particle sizes ranging from 2 to 25 μm in size were generated, which would be appropriate for thermoplastic polymer matrix composites prepared by powder processing. All specimens showed excellent thermooxidative stability, consistent with the aromatic imide structure.

The molecular design of the aromatic polyetherimide repeat unit was critical for the successful utilization of these semicrystalline high performance materials. The metba-linked TPER system when combined with the thermally stable s-biphenyl dianhydride (BPDA) produced a melting endotherm, T_m, at about 395°C, which was well within the thermal stability limitations of organic materials, i.e., less than or approximately 450°C. It was also demonstrated to be important to quantitatively endcap both ends of the chains at about 20-30,000 <M_n> with non-reactive phthalimide groups to achieve appropriate melt viscosities and good melt stability. This was done by off-setting the stoichiometry in favor of the diamine, reacting with a calculated amount of phthalic anhydride and imidizing in bulk above the Tg (≈210°C) at 300°C. These considerations allowed for remarkable melt stability in nitrogen at 430°C for at least 45 minutes, and importantly, repeated recrystallizations from the melt to afford tough, ductile semicrystalline films with excellent solvent resistance. If the macromolecular chains were not properly endcapped, it was demonstrated that viscosity increased rapidly at 430°C, suggesting reactions such as transimidization involving terminal amine end groups with in-chain imide segments and/or other side reactions, which quickly inhibited recrystallization, probably by reducing molecular transport processes.

In contrast, polyimides based upon the more rigid para-linked TPEQ did not demonstrate melt or flow characteristics below 400°C, and degraded around the T_m at about 470°C! The less thermally stable TPEQ-ODPA based polyimide did melt around 409°C, and lower molecular weight samples, e.g., 10,000 M_n, recrystallized from the melt after short melt times, but cast films were brittle. It was hypothesized that the weak link may be the relatively electron rich arylene ether bond derived from the ODPA dianhydride.

Several alkylated derivatives of TPER were synthesized in good yield by the reactions of alkylated resorcinol precursors with p-fluoronitrobenzene to produce dinitro compounds, which were subsequently reduced. These model diamines were then used to synthesize polyimides by the classical two step route. As expected, few of the polyimides derived from BPDA and these diamines displayed melting transitions (T_m), probably because of poor chain packing. However, they could have potential as new thermally stable membrane materials. Several amorphous polyimides prepared from 1,3-bis(p-aminophenoxy)-4-hexylbenzene were soluble in selected common organic solvents and could be cast into flexible films.