Aromatic polyetherimide

An all aromatic polyetherimide is made by Du Pont from reaction of pyromelUtic dianhydride and 4,4 -oxydianiline and is sold as Kapton. It possesses excellent thermal stabiUty, mechanical characteristics, and electrical properties, as indicated in Table 3. The high heat-deflection temperature of the resin limits its processibiUty. Kapton is available as general-purpose film and used in appHcations such as washers and gaskets. Often the resin is not used directly rather, the more tractable polyamide acid intermediate is appHed in solution to a surface and then is thermally imidi2ed as the solvent evaporates. 

Not all polyetherimides are limited by their tractability, however. Certain aromatic polyetherimides are characterized by a combination of properties that makes them potential engineering thermoplastics (90). One of these polymers contains an isopropylidene unit in the backbone to enhance the solubility. It is a mol ding material introduced by General Electric in 1981 and sold as Ultem resin. Attractive features include high temperature stability, flame resistance without added halogen or phosphoms, high strength, solvent resistance, hydrolytic stability, and injection moldability. 

Some examples of wholly aromatic polyetherimides were synthesised by workers at Liverpool University [42] and shown to be liquid crystalline [43]. The structures are given in Table 8. 

SYNTHESIS Aromatic polyetherimides are usually prepared from (a) bisphenoxide salts and aromatic dinitrobisimides via nucleophilic nitro-displacement reactions(b) two-step polycondensation of aromatic diamines and ether-dianhydrides in a polar aprotic solvent, followed by thermalor chemical cyclodehydration of the polyamic acid precursors and (c) one-step, high temperature solution polymerization of aromatic diamines and ether-dianhydrides in a phenolic solvent, removing water of condensation azeotropically. - Certain polyetherimides can also be s)mthesized via direct melt polymerization/ ... 

Huang, RY.M. and Feng, X. 1993. Dehydration of isopropanol by pervaporation using aromatic polyetherimide membrane. Sep. Set Technol. 28 2035-2048. 

I m pleased to tell you that aromatic polyetherimides have a bright future. Hard evidence in support of that viewpoint is the fact that General Electric Plastics has under construction a 74MM ULTEMS) capacity expansion at our site in Mt. Vernon, Indiana. We obviously believe strongly in the materials resulting from nucleophilic displacement of aromatic nitro groups. 

Thompson DS, Markoski LJ, Moore JS (1999) Rapid synthesis of hyperbranched aromatic polyetherimides. Macromolecules 32 4764—4768... 

Polotskaya G. A., Kuznetsov Y. P., Anikin A. V., Chemical Structure and Gas Selectivity of Membranes Manufactured from Aromatic Polyetherimides, Polym. Sci., 1992, 34(5 437. 

I itro-DisplacementPolymerization. The facile nucleophilic displacement of a nitro group on a phthalimide by an oxyanion has been used to prepare polyetherimides by heating bisphenoxides with bisnitrophthalimides (91). For example with 4,4 -dinitro monomers, a polymer with the Ultem backbone is prepared as follows (92). Because of the high reactivity of the nitro phthalimides, the polymerkation can be carried out at temperatures below 75°C. Relative reactivities are nitro compounds over halogens, Ai-aryl imides over A/-alkyl imides, and 3-substituents over 4-substituents. Solvents are usually dipolar aprotic Hquids such as dimethyl sulfoxide, and sometimes an aromatic Hquid is used, in addition. 

This scheme eliminates the process of converting bis(etherimide)s to bis(ether anhydride)s. When polyetherimides are fusible the polymerization is performed in the melt, allowing the monamine to distill off. It is advantageous if the amino groups of diamines are more basic or nucleophilic than the by-product monoamine. Bisimides derived from heteroaromatic amines such as 2-arninopyridine are readily exchanged by common aromatic diamines (68,69). High molecular weight polyetherimides have been synthesized from various N,lSf -bis(heteroaryl)bis(etherimide)s. 

Good electrical insulation properties with exceptional tracking resistance for an engineering thermoplastic and, in particular, for an aromatic polymer. In tracking resistance most grades are generally superior to most grades of polycarbonates, modified PPOs, PPS and the polyetherimides. 

Polyetherimides (PEI) are polyimides containing sufficient ether as well as other flexibi-lizing structural units to impart melt processability by conventional techniques, such as injection molding and extrusion. The commercially available PEI (trade name Ultem) is the polymer synthesized by nucleophilic aromatic substitution between 1,3-bis(4-nitrophthalimido) benzene and the disodium salt of bisphenol A (Eq. 2-209) [Clagett, 1986]. This is the same reaction as that used to synthesize polyethersulfones and polyetherketones (Eq. 2-206) except that nitrite ion is displaced instead of halide. Polymerization is carried out at 80-130°C in a polar solvent (NMP, DMAC). It is also possible to synthesize the same polymer by using the diamine-dianhydride reaction. Everything being equal (cost and availability of pure reactants), the nucleophilic substitution reaction is probably the preferred route due to the more moderate reaction conditions. 

Condensation of Dianhydrides with Diamines. The preparation of polyetherimides by the reaction of a diamine with a dianhydride has advantages over nitro-displacement polymerization sodium nitrite is not a by-product and thus does not have to be removed from the polymer, and a dipolar aprotic solvent is not required, which makes solvent-free melt polymerization a possibility. Aromatic dianhydride monomers (8) can be prepared from IV-substituted nitrophthalimides by a three-step sequence that utilizes the nitro-displacement reaction in the first step, followed by hydrolysis and then ring closure. For the 4-nitro compounds, the procedure is as follows. 

In recent years, remarkable progress has been made in the syntheses of aromatic and heterocyclic polymers to search a new type of radiation resistant polymers. Sasuga and his coworkers extensively investigated the radiation deterioration of various aromatic polymers at ambient temperature [55-57] and reported the order of radiation resistivity evaluated from the changes in tensile properties as follows polyimide > polyether ether ketone > polyamide > polyetherimide > polyarylate > polysulfone. 

Many computational studies of the permeation of small gas molecules through polymers have appeared, which were designed to analyze, on an atomic scale, diffusion mechanisms or to calculate the diffusion coefficient and the solubility parameters. Most of these studies have dealt with flexible polymer chains of relatively simple structure such as polyethylene, polypropylene, and poly-(isobutylene) [49,50,51,52,53], There are, however, a few reports on polymers consisting of stiff chains. For example, Mooney and MacElroy [54] studied the diffusion of small molecules in semicrystalline aromatic polymers and Cuthbert et al. [55] have calculated the Henry s law constant for a number of small molecules in polystyrene and studied the effect of box size on the calculated Henry s law constants. Most of these reports are limited to the calculation of solubility coefficients at a single temperature and in the zero-pressure limit. However, there are few reports on the calculation of solubilities at higher pressures, for example the reports by de Pablo et al. [56] on the calculation of solubilities of alkanes in polyethylene, by Abu-Shargh [53] on the calculation of solubility of propene in polypropylene, and by Lim et al. [47] on the sorption of methane and carbon dioxide in amorphous polyetherimide. In the former two cases, the authors have used Gibbs ensemble Monte Carlo method [41,57] to do the calculations, and in the latter case, the authors have used an equation-of-state method to describe the gas phase. 

Specialty polymers achieve very high performance and find limited but critical use in aerospace composites, in electronic industries, as membranes for gas and liquid separations, as fire-retardant textile fabrics for firefighters and race-car drivers, and for biomedical applications (as sutures and surgical implants). The most important class of specialty plastics is polyimides. Other specialty polymers include polyetherimide, poly(amide-imide), polybismaleimides, ionic polymers, polyphosphazenes, poly(aryl ether ketones), polyarylates and related aromatic polyesters, and ultrahigh-molecular-weight polyethylene (Fig. 14.9). 

According to literary data, the following mixtures of aromatic/aliphatic-aromatic hydrocarbons were separated toluene/ n-hexane, toluene/n-heptane, toluene/n-octane, toluene/f-octane, benzene/w-hexane, benzene/w-heptane, benzene/toluene, and styrene/ethylbenzene [10,82,83,109-129]. As membrane media, various polymers were used polyetherurethane, poly-esterurethane, polyetherimide, sulfonyl-containing polyimide, ionicaUy cross-linked copolymers of methyl, ethyl, n-butyl acrylate with acrilic acid. For example, when a composite polyetherimide-based membrane was used to separate a toluene (50 wt%)/n-octane mixture, the flux Q of 10 kg pm/m h and the separation factor of 70 were achieved [121]. When a composite mebrane based on sulfonyl-containing polyimide was used to separate a toluene (1 wt%)/ -octane mixture, the flux 2 of 1.1 kg pm/m h and the separation factor of 155 were achieved [10]. When a composite membrane based on ionically cross-linked copolymers of methyl, ethyl, w-butyl acrylate with acrilic acid was used to separate toluene (50 wt%)//-octane mixture, the flux Q of 20-1000 kg pm/m h and the separation factor of 2.5-13 were achieved [126,127]. 

More recently it has been shown that some of the polyetherimides derived from bis(ether anhydride)s and aromatic diamines containing more than one ether group show crystallinity and that their melting temperatures are in a range of 300 to 400 °C [36, 50],... 

Materials. The amorphous matrix polymer was polyetherimide (Ultem 1000) sold by the General Electric Company. The semicrystalline matrices were PEEK and a high molecular weight polyphenylenesulfide (PPS) provided by ICI and Phillips Petroleum Co. (Barthesville, OK.), respectively. The reinforcing phase was one of several LCPs a liquid crystalline aromatic copolyester consisting of 73 %... 

Polyetherimide has a chemical structure based on repeating aromatic imide and ether units. High performance strength characterisitics at elevated temperatures are provided by rigid imide units, while the ether linkages confer the chain flexibility necessary for good melt processing and flow. 

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