Amic acids

A. Carry out the following preliminary test. Dissolve a drop or a few small crystals of the compound in 1 ml. of rectified spirit (95 per cent, ethanol) and add 1 ml. of iV hydrochloric acid. Note the colour produced when 1 drop of 5 per cent, ferric chloride solution is added to the solution. If a pronounced violet, blue, red or orange colour is produced, the hydrox amic acid test described below is not applicable and should not be used. 

VDP Polyimides. Polyimide films have also been prepared by a kind of VDP (16). The poly(amic acid) layer is first formed by the coevaporation and condensation of two monomers, followed by copolymerization on the substrate. The imidization is carried out in a separate baking step (see POLYIMIDES). 

Synthesis and Properties. Several methods have been suggested to synthesize polyimides. The predominant one involves a two-step condensation reaction between aromatic diamines and aromatic dianhydrides in polar aprotic solvents (2,3). In the first step, a soluble, linear poly(amic acid) results, which in the second step undergoes cyclodehydration, leading to an insoluble and infusible PL Overall yields are generally only 70—80%. 

A viscous solution of poly(amic acid) can be processed into films, fibers, and coatings, and the final product undergoes thermal cyclo dehydration. 

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). 

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. 

Monomer Reactivity. The poly(amic acid) groups are formed by nucleophilic substitution by an amino group at a carbonyl carbon of an anhydride group. Therefore, the electrophilicity of the dianhydride is expected to be one of the most important parameters used to determine the reaction rate. There is a close relationship between the reaction rates and the electron affinities, of dianhydrides (12). These were independendy deterrnined by polarography. Stmctures and electron affinities of various dianhydrides are shown in Table 1. 

Effect of Solvents. The most commonly used solvents in poly(amic acid) preparation are dipolar amide solvents such as DMAc and NMP. 

In addition, however, several minor but important side reactions concurrently proceed with the main reaction. These side reactions may become significant under certain conditions, particularly when the main reaction is slow because of low monomer reactivities or low concentrations. The principal pathways involved in the formation of poly(amic acid) are as shown in Eigure 1. 

The reverse reaction is an intramolecular acidolysis of amide group by the o-carboxyhc acid to reform anhydride and amine. This unique feature is the result of an ortho neighboring effect. In contrast, the acylation of an amine with ben2oic anhydride is an irreversible reaction under the same reaction conditions. The poly(amic acid) stmcture (8) can be considered as a class of polyamides. Aromatic polyamides that lack ortho carboxylic groups are very... 

The effect of the conformation of amic acid on the imidi2ation rate is also consistent with the observation that the thermal cycli2ation of model compounds, N-substituted phthalamic acids, is strongly influenced by the steric effect imposed by N-substituents (18). 

AijAT-dicyclohexylcarhodiimide (DCC) also leads to essentially quantitative conversion of amic acids to isoimides, rather than imides (30,31). Combinations of trifluoroacetic anhydride—triethjlarnine and ethyl chi oroform a te—triethyl amine also result in high yields of isoimides (30). A kinetic study on model compounds has revealed that isoimides and imides are formed via a mixed anhydride intermediate (12) that is formed by the acylation of the carboxylic group of amic acid (8). 

Fig. 2. Cyclization of amic acid to imides or isoimides via (12). Formation of the mixed anhydride intermediate (12) is shown in text.

Bonnett et alJ observed the formation of the pyrrolidone hydrox-amic acid (66) as a by-product in the alkaline hydrolysis of a 2-cyano-nitrone (69). This displacement of cyanide by hydroxyl seems to be quite general. 

Syntheses of 4-substituted isoxazoles from -diketones and hydrox-amic acid chlorides were reported earlier. A recent investigation has realt with the behavior in this reaction of malonic ester. ... 

Figure 5.31 Amic acid formation and imide cyclization.

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