Polyimide production

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. 

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 /V,/V-dimethy1 acetamide [127-19-5] (DMAc) or /V-methy1pyrro1idinone [872-50-4] (NMP) to form apoly(amic acid), which is then cycHzed into the polyimide product. The reaction of pyromeUitic dianhydride [26265-89-4] (PMDA) and 4,4 -oxydiani1ine [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. 

A dianhydride and diamine in the presence of an acid catalyst produces an intermediate polyimide product an amino-terminated siloxane is added at a reduced temperature... 

Adhesive characteristics of thin SPI-100 films could not be measured directly because adhesive forces are generally larger than cohesive forces. To obtain some information on adhesion values, thin high molecular weight SPI-100 films on substrates were overcoated with about. 1 mm of a commercially available polyimide (Product A) to provide greater cohesive strength than can be obtained with SPI-100 alone. The combined layers were then pulled in an Instron tester giving the results shown in Table II which also includes the values for commercial products A and B. 

In the second step, polyamic acid is cyclo-dehy-drated at elevated temperatures (thermal imidization) or in the presence of a cyclizing agent (chemical imidization). Advantages of this method over one-step polymerization are the use of less toxic solvents and direct processing of soluble polyamic acids to form the final polyimide products in the form of films or fibers by thermal imidization. However, the storage instability of polyamic acid intermediates and the control of thermal imidization are still important issues [28]. A detail description of the thermal and chemical imidization of poly(amic acid) is given below. 

The first reported synthesis of an aromatic polyimide was in 1908 (1). However, much of the credit for the development and commercialization of polyimide products goes to DuPont, who benchmarked thi.s endeavor in the 1960s with the release of Kapton H film, Vespel molded parts, and Pyre-ML wire varnish (2). This effort inspired other researchers in academia, industry, and government laboratories to piusue the chemistry, fabrication, and appUcations of pol3rimides not envisioned several decades ago. There are several excellent books that address the extensive topic of polyimides (3-6). This article provides an overview of the field of polyimides from ssmthesis and basic kinetic behavior to fabrication and articles of manufacture. 

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] ... 

This polymerization is carried out in the two stages indicated above precisely because of the insolubility and infusibility of the final product. The first-stage polyamide, structure [IX], is prepared in polar solvents and at relatively low temperatures, say, 70°C or less. The intermediate is then introduced to the intended application-for example, a coating or lamination-then the second-stage cyclization is carried out at temperatures in the range 150-300°C. Note the formation of five-membered rings in the formation of the polyimide, structure [X], and also that the proportion of acid to amine groups is 2 1 for reaction (5.II). 

Polyimides for use ia molded products and high temperature films can be produced by the reaction of pyromelHtic dianhydride [89-32-7] and 4,4 -diaminodiphenyl ether [13174-32-8] ia DMAC to form a polyamide that can be converted iato a polyimide (13). DMAC can also be used as a spinning solvent for polyimides. AdditionaUy, polymers containing over 50% vinyHdene chloride are soluble up to 20% at elevated temperatures ia DMAC. Such solutions are useful ia preparing fibers (14). 

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. 

A variety of cellular plastics exists for use as thermal iasulation as basic materials and products, or as thermal iasulation systems ia combination with other materials (see Foamed plastics). Polystyrenes, polyisocyanurates (which include polyurethanes), and phenoHcs are most commonly available for general use, however, there is increasing use of other types including polyethylenes, polyimides, melamines, and poly(vinyl chlorides) for specific appHcations. 

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). 

The reactions of primary amines and maleic anhydride yield amic acids that can be dehydrated to imides, polyimides (qv), or isoimides depending on the reaction conditions (35—37). However, these products require multistep processes. Pathways with favorable economics are difficult to achieve. Amines and pyridines decompose maleic anhydride, often ia a violent reaction. Carbon dioxide [124-38-9] is a typical end product for this exothermic reaction (38). 

Polyimides (PI) are polycondensation products (1) prepared from derivatives of tetracarboxylic acids and primary diamines (1—5). Descriptions of self-polycondensation polymers (2) based on aminodicarboxylic acid derivatives are also found in the literature (6—9). 

Semicommercial production of 3,3/4,4 -biphenyltetracarboxyhc dianhydride [2420-87-3] in the United States has been announced by Occidental Chemical Corp. (74). This polyimide resin intermediate is prepared by dehalogenative dimerization of 4-chlorophthalate salts (75) or by oxidative coupling of phthalate esters (76). 

The reaction product of 4,4 -bismaleimidodiphenylmethane and 4,4 -diaminophenylmethane, known as Kerimide 601 [9063-71-2] is prepolymerized to such an extent that the resulting prepolymer is soluble in aprotic solvents such as /V-methy1pyrro1idinone [872-50-4] dimethylformamide [68-12-2] and the like, and therefore can be processed via solution techniques to prepreg. Kerim ide 601 is mainly used in glass fabric laminates for electrical appHcations and became the industry standard for polyimide-based printed circuit boards (32). 

In 1990 the majority of U.S. PCB production resulted from subtractive or print-and-etch processing additive processes were less than 6% of the total multilayer boards accounted for 55.8%. The ratio of rigid to flexible surface areas plated is about 15 1. High performance plastics including polyimide. Teflon, and modified epoxy comprised 6% of the market ( 324 million) flexible circuits were 6.6% ( 360 million) (42). 

Commonly accepted practice restricts the term to plastics that serve engineering purposes and can be processed and reprocessed by injection and extmsion methods. This excludes the so-called specialty plastics, eg, fluorocarbon polymers and infusible film products such as Kapton and Updex polyimide film, and thermosets including phenoHcs, epoxies, urea—formaldehydes, and sdicones, some of which have been termed engineering plastics by other authors (4) (see Elastol rs, synthetic-fluorocarbon elastol rs Eluorine compounds, organic-tdtrafluoroethylenecopolyt rs with ethylene Phenolic resins Epoxy resins Amino resins and plastics). 

Other Polyimides. In 1979, Rohm Haas introduced Kamax resin, which was thought to be an /V-methylamine imidization product of poly(methyl methacrylate) (118). The product was then withdrawn, but was reintroduced in the late 1980s. The partly imidized resins are similar to poly(methyl methacrylate) but have a higher glass-transition temperature. 

The total production volume of these various polyimides is low (<1000 t/yr). Prices tend to be high for example, some Kapton film topics can mn in excess of 176/kg. 

---