Polyimides commercial

Experimental polyimides Commercial polyimides O Polyamide-imides — Free water... 

Many cellular plastics that have not reached significant commercial use have been introduced or their manufacture described in Hterature. Examples of such polymers are chlorinated or chlorosulfonated polyethylene, a copolymer of vinyUdene fluoride and hexafluoropropylene, polyamides (4), polytetrafluoroethylene (5), styrene—acrylonitrile copolymers (6,7), polyimides (8), and ethylene—propylene copolymers (9). 

Polyimides (PI) were among the eadiest candidates in the field of thermally stable polymers. In addition to high temperature property retention, these materials also exhibit chemical resistance and relative ease of synthesis and use. This has led to numerous innovations in the chemistry of synthesis and cure mechanisms, stmcture variations, and ultimately products and appHcations. Polyimides (qv) are available as films, fibers, enamels or varnishes, adhesives, matrix resins for composites, and mol ding powders. They are used in numerous commercial and military aircraft as stmctural composites, eg, over a ton of polyimide film is presently used on the NASA shuttle orbiter. Work continues on these materials, including the more recent electronic apphcations. 

Membrane modules have found extensive commercial appHcation in areas where medium purity hydrogen is required, as in ammonia purge streams (191). The first polymer membrane system was developed by Du Pont in the early 1970s. The membranes are typically made of aromatic polyaramide, polyimide, polysulfone, and cellulose acetate supported as spiral-wound hoUow-ftber modules (see Hollow-FIBERMEMBRANEs). 

Other Polymers. Besides polycarbonates, poly(methyl methacrylate)s, cycfic polyolefins, and uv-curable cross-linked polymers, a host of other polymers have been examined for their suitabiUty as substrate materials for optical data storage, preferably compact disks, in the last years. These polymers have not gained commercial importance polystyrene (PS), poly(vinyl chloride) (PVC), cellulose acetobutyrate (CAB), bis(diallylpolycarbonate) (BDPC), poly(ethylene terephthalate) (PET), styrene—acrylonitrile copolymers (SAN), poly(vinyl acetate) (PVAC), and for substrates with high resistance to heat softening, polysulfones (PSU) and polyimides (PI). 

Carboxyhc acids react with aryl isocyanates, at elevated temperatures to yield anhydrides. The anhydrides subsequently evolve carbon dioxide to yield amines at elevated temperatures (70—72). The aromatic amines are further converted into amides by reaction with excess anhydride. Ortho diacids, such as phthahc acid [88-99-3J, react with aryl isocyanates to yield the corresponding A/-aryl phthalimides (73). Reactions with carboxyhc acids are irreversible and commercially used to prepare polyamides and polyimides, two classes of high performance polymers for high temperature appHcations where chemical resistance is important. Base catalysis is recommended to reduce the formation of substituted urea by-products (74). 

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 ... 

Since successful commercialization of Kapton by Du Pont Company in the 1960s (10), numerous compositions of polyimide and various new methods of syntheses have been described in the Hterature (1—5). A successful result for each method depends on the nature of the chemical components involved in the system, including monomers, intermediates, solvents, and the polyimide products, as well as on physical conditions during the synthesis. Properties such as monomer reactivity and solubiHty, and the glass-transition temperature,T, crystallinity, T, and melt viscosity of the polyimide products ultimately determine the effectiveness of each process. Accordingly, proper selection of synthetic method is often critical for preparation of polyimides of a given chemical composition. 

Relatively few processible polyimides, particularly at a reasonable cost and iu rehable supply, are available commercially. Users of polyimides may have to produce iutractable polyimides by themselves in situ according to methods discussed earlier, or synthesize polyimides of unique compositions iu order to meet property requirements such as thermal and thermoxidative stabilities, mechanical and electrical properties, physical properties such as glass-transition temperature, crystalline melting temperature, density, solubility, optical properties, etc. It is, therefore, essential to thoroughly understand the stmcture—property relationships of polyimide systems, and excellent review articles are available (1—5,92). 

Plastics. Almost all commercial plastics find some use both dry and lubricated for sliding at low speeds and light loads the most commonly used thermoplastics are nylon, acetal resins, and polytetrafluoroethylene (PTFE). Typical thermosetting resins for bearing appHcations are phenoHcs, polyesters, and polyimides. Table 8 compares the characteristics of plastic bearing materials with those of graphite, wood, and mbber which find use in somewhat similar appHcations. 

Polyetherimide Resins. Polyetherknide resins (PEI) (7) were commercialized during the 1980s (see Polyimides). They ate produced by an unusual nucleophilic substitution process ... 

Bis-maleimide resins composed of BMI and diamines have been reported in the early 1960s in the patent literature. Since that time, a number of patents have appeared describing improvements in their properties and uses [3]. Although many bis-maleimide resins are commercially developed, relatively few reports of their use as adhesives are to be found in scientific journals [4-10]. Improvements of maleimide resins are mirrored in the improvements of thermosetting polyimides. For example, the method of in situ polymerization of monomer reactants (PMR method) was developed [6]. 

Because of this continued emphasis on adhesive bonding technology development over the years, the airframes of modem front-line aircraft such as the B-2 bomber and the F-117 and F-22 fighters are largely structurally bonded advanced composites. They tend to be comprised of materials that are more advanced (expensive) than commercial aircraft such as carbon and boron fiber reinforcements with cyanate esters, bismaleimides, polyimides or other high-temperature resin matrices and adhesives. 

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. 

Different dianhydrides have been syndiesized or are commercially available, and some structures arc shown in Fig. 5.9.64-66 An improved method for preparation of cyclobutanetetracarboxylic dianhydride (CBDA) by photochemical dimerization of die maleic anhydride has been developed by Nissan.67 The polyimide obtained by condensation of CBDA widi oxydianiline gives a transparent and colorless material. The transmittance of 50-pm-thick film is 82% and the UV cutoff is 310 nm. 

In 1977, Parshall and co-workers published their work on the separation of various homogeneous catalysts from reaction mixtures.[46] Homemade polyimide membranes, formed from a solution of polyamic acid were used. After reaction the mixture was subjected to reverse osmosis. Depending on the metal complex and the applied pressure, the permeate contained 4-40% of the original amount of metal. This publication was the beginning of research on unmodified or non-dendritic catalysts separated by commercial and homemade membranes. 

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