Pyromellitic dianhydride, polyimide

Systems that employed HREELS for interfacial-composition determinations included poly(ethylene oxide)-polystyrene diblock copolymer on Si wafers formaldehyde poly(oxymethylene) films on Cu(lOO) and Lang-muir-Blodgett films of 4,4 -oxydianiline-pyromellitic dianhydride polyimide on Au and on highly ordered pyrolytic graphite. ... 

Xu and Coleman studied 6FDA (2,2 -bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride)-pMDA (pyromellitic dianhydride) polyimide films irradiated by an ion beam [84]. A beam of 140 keV N ions with a low-current density was used, and three irradiation fluences (2 x 10 cm , 1 x 10 cm , and 5 x 10 cm ) were chosen. It was reported that even a small dose altered the microstructure of the surface layer. The AFM analysis of those films showed that low-fluence irradiation induced microvoids in the surface layer of the polymer, and high-fluence irradiation resulted... 

Aromatic polyimides are the first example we shall consider of polymers with a rather high degree of backbone ring character. This polymer is exemplified by the condensation product of pyromellitic dianhydride [Vll] and p-amino-aniline [Vlll] ... 

Uses. Pyromellitic dianhydride imparts heat stabUity in applications where it is used. Its relatively high price limits its use to these applications. The principal commercial use is as a raw material for polyimide resins (see POLYIMIDES). These polypyromellitimides are condensation polymers of the dianhydride and aromatic diamines such as 4, -oxydianifine ... 

A considerable number of non-cross-linked aromatic and heterocyclic polymers has been produced. These include polyaromatic ketones, aromatic and heterocyclic polyanhydrides, polythiazoles, polypyrazoles, polytriazoles, poly-quinoxalines, polyketoquinolines, polybenzimidazoles, polyhydantoins, and polyimides. Of these the last two have achieved some technical significance, and have already been considered in Chapters 21 and 18 respectively. The most important polyimides are obtained by reacting pyromellitic dianhydride with an aromatic diamine to give a product of general structure (Figure 29.17). 

Potyimides obtained by reacting pyromellitic dianhydride with aromatic amines can have ladder-like structures, and commercial materials are available which may be used to temperatures in excess of 300°C. They are, however, somewhat difficult to process and modified polymers such as the polyamide-imides are slightly more processable, but with some loss of heat resistance. One disadvantage of polyimides is their limited resistance to hydrolysis, and they may crack in aqueous environments above 100°C. 

Polyimide-clay nanocomposites constitute another example of the synthesis of nanocomposite from polymer solution [70-76]. Polyimide-clay nanocomposite films were produced via polymerization of 4,4 -diaminodiphenyl ether and pyromellitic dianhydride in dimethylacetamide (DMAC) solvent, followed by mixing of the poly(amic acid) solution with organoclay dispersed in DMAC. Synthetic mica and MMT produced primarily exfoliated nanocomposites, while saponite and hectorite led to only monolayer intercalation in the clay galleries [71]. Dramatic improvements in barrier properties, thermal stability, and modulus were observed for these nanocomposites. Polyimide-clay nanocomposites containing only a small fraction of clay exhibited a several-fold reduction in the... 

The kinetics of PAA, synthesized from 4,4 -oxydianiline and pyromellitic dianhydride, solid-state imidization both in filler absence and with addition of 2 phr Na+-montmorillonite was studied [1], The nanofiller was treated by solution of P-phenylenediamine in HC1 and then washed by de-ionized water to ensure a complete removal of chloride ions. The conversion (imidization) degree Q was determined as a function of reaction duration t with the aid of Fourier transformation of IR-spectra bands 726 and 1014 cm 1. The samples for FTIR study were obtained by spin-coating of PAA/Na+-montmorillonite mixture solution in N,N-dimethylacetamide on KBr disks, which then were dried in vacuum for 48 h at 303 K. It was shown, that the used in paper [1] method gives exfoliated nanocomposites. The other details of nanocomposites polyimid/Na+-montmorillonite synthesis and study in paper [1] were adduced. The solid-state imidization process was made at four temperatures 7) 423, 473, 503 and 523 K. 

Angeltr—>has briefly reported in a patent the addition of metal ions to several types of polyimides. The object of the invention was a process for forming particle-containing (transparent polyimide shaped structures. Unlike the work discussed previously, all of the metals were added in the form of coordination complexes rather than as simple anhydrous or hydrated salts. The properties of only one film (e.g. cast from a N,N-dimethylformamide(DMF) solution of 4,4 -diaminodiphenyl methane, pyromellitic dianhydride and bis(acetylacetonato)-... 

Further work in this area is underway employing polyamic acid systems which are known to produce higher viscosity solutions (e.g. polyimides derived from 4,4 -oxydianiline and either BTDA or pyromellitic dianhydride). This is being carried out in the belief that higher viscosity solutions will give rise to higher quality, less brittle films and will, thereby, enable a broader spectrum of metal systems to be studied regarding the adhesive and electrical conductance properties of metal ion filled polyimides. 

Benzenetetracarboxylic dianhydride (pyromellitic dianhydride) is a typical bifunctional acid anhydride, and it is a useful raw material for preparing many useful chemicals. Polyimides and polyimidazopyrrolons prepared from this dianhydride have excellent heat and chemical resistance, as well as excellent mechanical and electrical properties. Pyromellitic dianhydride is produced by the oxidation of 1,2,4,5-tetraalkylbenzenes such as 1,2,4,5-tetramethylbenzene (commonly known as durene) and 4,6-diisopro-pyl-l,3-dimethylbenzene. Durene, in particular, is a fundamental raw material for the production of the dianhydride 1-8). 

Preparation of a Polyimide from Pyromellitic Dianhydride and 4,4 -0xydianiline by Polycyclocondensation... 

The polyimide is formed by the thermal polycyclocondensation of the poly(amide acid). For this purpose, 5 ml of poly(amide acid) solution are placed on a watch glass (diameter 10 cm) and kept in a vacuum oven at 50 °C for 24 h.The solvent evaporates and at the same time cyclization to the polyimide takes place the resulting film is insoluble in dimethylformamide.The formation of the polyimide can be followed by IR spectroscopy the NH-band at 3250 cm disappears while imide bands appear at 1775 and 720 cm" Once the initial drying process has raised the solid content to 65-75%, the polyimide formation can be accelerated by heating the poly(amide acid) film to 300 °C in a vacuum oven for about 45 min.The polyimide made from pyromellitic dianhydride and 4,4 -oxydianiline exhibits long-term stability in air above 200 °C. 

Next we consider the dispersion polymerization by polyaddition. In a typical method to prepare polyimide particles, polyamic acid solution is first obtained by coupling of pyromellitic dianhydride and oxy-dianiline, and then by heating the solution. The condensation reaction on heating causes crystallization of polyimide in a spherical form (Fig. 11.2.5, left) (33). However, on the contrary to this conventional method, polyamic acid microspheres could be obtained by dispersion polymerization if an appropriate medium is chosen (34). When a solvent that has a solubility parameter around 17 Mpa is used, submicrometer-sized monodisperse polyamic acid parti-... 

Hasegawa et al. (1) prepared conjugated pyromellitic dianhydride polyazo-methines, (I), and converted them into a pyromellitic polyimide ladder, ( ), by reacting with two equivalents of benzidine. 

TABLE 1. Physical Properties of d-Polyimides Prepared by Condensing Pyromellitic Dianhydride with Deuterated o-Tolidine and then Heating to 200-300°C... 

Fig. 7. Polymer solution stability of pyromellitic dianhydride/aniline phthalein based polyimide precursor in dimethylacetamide at ambient temperature. [C] = 0.5 wt%, ( ) poly(amic methyl ester), ( ) polyfamic acid) [66]...

A new synthetic, low temperature approach to polyimides has recently been reported [112]. The synthetic scheme is based on dicyanomethylidene phthalide derivatives, which are synthetic analogs to the corresponding anhydrides. As shown in Scheme 33, pyromellitic dianhydride can be readily converted to the... 

Aromatic polyimides have excellent thermal stability in addition to their good electrical properties, light weight, flexibility, and easy processability. The first aromatic polyimide film (Kapton, produced by DuPont) was commercialized in the 1960s and has been developed for various aerospace applications. The structure of a typical polyimide PMDA/ODA prepared from pyromellitic dianhydride (PMDA) and 4,4 -oxydianiline (ODA), which has the same structure as Kapton, is shown in (1). Aromatic polyimides have excellent thermal stability because they consist of aromatic and imide rings. 

Relative to microelectronic applications, the out-of-plane dielectric constant for BPDA-PFMB films measmed after aging at 50% relative humidity for 48 h at 23°C was between 2.8 and 2.9 (0.1 kHz to 1 MHz) (ASTM D-150-81These values are considerably lower than that of commercial polyimides such as PMDA-ODA (pyromellitic dianhydride, PMDA) (s = 3.5 at 1 kHz and 3.3 at 10 MHz). The dielectric constant and tan 8 (dissipation factor) were temperature- and frequency-dependent. The dielectric constant, which was independent of temperature until near 210°C increased above this point until a frequency-dependent maximum was reached at about 290°C. The dissipation factor, which was also independent of temperatme below 200°C, underwent a rapid increase with no maximum between 200 and 400°C owing to ion conductivity. The temperatme at which this increase occurred increased as the frequency increased. The films also... 

The two-step poly(amic acid) process is the most commonly practiced procedure. In this process, a dianhydride and a diamine react at ambient temperature in a dipolar aprotic solvent such as N,N- dimethyl acetamide [127-19-5] (DMAc) or N-methylpyrrolidinone [872-50 4] (NMP) to form apoly(amic acid), which is then cyclized into the polyimide product. The reaction of pyromellitic dianhydride [26265-89 4] (PMDA) and 4,4 -oxydianiline [101-80-4] (ODA) proceeds rapidly at room temperature to form a viscous solution of poly(amic acid) (5), which is an ortho-carboxylated aromatic polyamide. 

Abstract—The adhesion of pyromellitic dianhydride-oxydianiline (PMDA-ODA) polyimide to fluorine-contaminated silicon dioxide (F-SiO,) with y-aminopropyllriethoxysilane (APS) adhesion promoter has been studied as a function of the peel ambient humidity. The peel strength was not affected by the change in peel ambient relative humidity (RH) from 11-17% to 35-60% when APS was used at the interface. Without APS, the adhesion degraded significantly with this change in RH. It was found that although the dip application of APS caused the removal of about 80% of the initial atomic percentage of fluorine on the surface, it could not be totally removed even after several days in water at elevated temperature. 

Abstract—The effects of both y-aminopropyltriethoxysilane (APS) and elevated temperature and humidity (T H) exposure on the adhesion of pyromellitic dianhydride-oxydianiline polyimide to SiO , AkOi, and MgO were studied using XPS, SEM, and peel test. Adhesion and T H stability of PMDA-ODA on Si02 is significantly improved when APS is used at the interface, while no significant improvement is observed for AkO, or MgO. XPS analysis of the surfaces showed no retention of APS on AkO, or MgO, while Si02 did retain APS, as is expected. The APS retention is affected by surface treatment of the oxide prior to APS application. 

Adhesion of polyimides to inorganic substrates is of great importance to the microelectronics industry [1, 2]. The polyimide films are deposited most often by spin coating the polyamic acid (PAA) usually from a TV-methylpyrrolidone (NMP) solution onto the substrate surface followed by thermal imidization at temperatures up to 400<>C. The most studied polyimide is the pyromellitic dianhydride-oxydianiline (PMDA-ODA), which exhibits excellent mechanical and dielectric properties, but not so good adhesion characteristics. The latter has been generally overcome by application of an adhesion promoter, such as y-aminopropyltriethoxysilane [3-7]. The reactions of APS (coated from water solution) with the silicon dioxide surface as well as with polyamic acid have been well characterized by Linde and Gleason [4] however, we do not have such detailed information available on APS interaction with other ceramic surfaces. 

A variety of methods are known for the synthesis of polyimides and other condensation polymers, however, the application of high pressure has seldom appeared in the literature to date. Early in 1969 Morgan and Scott reported on the high-pressure polycondensation and simultaneous hot-pressing of intractable polybenzimidazopyrrolone, that is infusible and insoluble, directly from the combination of 3,3f,4,4f-tetraaminobiphenyl and pyromellitic dianhydride (Eq.6) [29,30]. 

As mentioned before, the first generation of fully aromatic homopolyimides, could be used in a few applications because they had to be applied in the form of soluble polyamic acids, and this limited the materials to be transformed almost exclusively into films or coatings [2,10]. They all had to be synthesized by a two-step method, as exemplified for an aromatic polyimide from pyromellitic dianhydride in Scheme 1. The method involves the synthesis of a soluble polyamic acid, which, after shaping, can be converted to the related polyimide by a thermal or a chemical treatment. Abundant literature is available on the methods and the mechanisms involved in the synthesis of these polymers [3,4,11-13]. 

Polyimide surface modification by a wet chemical process is described. Poly(pyromellitic dianhydride-oxydianiline) (PMDA-ODA) and poly(bisphenyl dianhydride-para-phenylenediamine) (BPDA-PDA) polyimide film surfaces are initially modified with KOH aqueous solution. These modified surfaces are further treated with aqueous HC1 solution to protonate the ionic molecules. Modified surfaces are identified with X-ray photoelectron spectroscopy (XPS), external reflectance infrared (ER IR) spectroscopy, gravimetric analysis, contact angle and thickness measurement. Initial reaction with KOH transforms the polyimide surface to a potassium polyamate surface. The reaction of the polyamate surface with HC1 yields a polyamic acid surface. Upon curing the modified surface, the starting polyimide surface is produced. The depth of modification, which is measured by a method using an absorbance-thickness relationship established with ellipsometry and ER IR, is controlled by the KOH reaction temperature and the reaction time. Surface topography and film thickness can be maintained while a strong polyimide-polyimide adhesion is achieved. Relationship between surface structure and adhesion is discussed. 

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