Thermal imidation

Conditions for low temperature solution polymerizations of pyromellitic dianhydride (PMDA) have been developed for a wide variety of aromatic 1,4-phenylene [54, 55] and 4,4 -biphenylene [56-58] diamine monomers in a number of aprotic solvents to give high molecular weight prepolymers referred to as polyamic acids. Since the imidized structures are insoluble, they must be processed in the form of their polyamic acids which are subsequently imidized thermally or by chemical dehydrating agents. Although this procedure is acceptable for thin film or fibers, the fabrication of thick parts is complicated by the water of imidization. 

Bessonov, M. I. Koton, M. M. Kudryavtsev, V. V. Laius, L. A. Poly-imides. Thermally Stable Polymers Consultants Bureau New York, 1987. 

Since the polyamic acid is imidized thermally,it was important to determine the thickness loss upon imidization. This was done for a number of films and the data is plotted in Figure 6. It was seen that in almost all the cases,the thickness change was about 30%. This was useful in altering initial polyamic acid thicknesses to suit the device needs,and in a few cases to form multiple layers of imides on devices. 

Copoly(amide-imides) comprise an important class of copolyimides that have been developed into a commercial product. Incorporating the amide linkage into the PI makes the polymer more tractable than simple Pis, but involves a loss in thermal stabiUty. However, copoly(amide—imides) still possess quite good thermal stabiUties, intermediate between those of polyamides and Pis (12). They are relatively inexpensive to synthesize. 

Poly(phenylquinoxaline—arnide—imides) are thermally stable up to 430°C and are soluble in polar organic solvents (17). Transparent films of these materials exhibit electrical insulating properties. Quinoxaline—imide copolymer films prepared by polycondensation of 6,6 -meth5lene bis(2-methyl-3,l-benzoxazine-4-one) and 3,3, 4,4 -benzophenone tetracarboxyUc dianhydride and 4,4 -oxydianiline exhibit good chemical etching properties (18). The polymers are soluble, but stable only up to 200—300°C. 

Polypyromehitimide films based on cyclotriphosphazene and bisaspartimide-derived diamines have shown thermal stabiUties up to 800°C and char yields of 56—68% in N2 and 24% in air (29). High strength fine- and heat-resistant imide resins containing cyclotriphosphazene and... 

Research activities in the area of PODs containing aromatic groups have been centered around the production of highly processible, soluble, and thermally stable polymers. In this particular class of PODs, the imide-and phenylene-containing backbones have been widely explored. 

These materials also have high thermal and oxidative stabiHty. Flexible segments such as amide siloxane can be incorporated into the imide-based stmcture for hot melt or injection appHcations. General Electric (GE) and Hoechst-Celanese are suppHers of these high performance plastics. 

Azolinones, azolinethiones, azolinimines N-Oxides, N-imides, N-ylides of azoles Thermal and Photochemical Reactions Formally Involving No Other Species 2.1 Thermal fragmentation... 

Tsai then applied thick films of the polyamic acid of PMDA and 4-BDAF to polished silver substrates and thermally imidized the films. The substrates were immersed into liquid nitrogen, causing the films to delaminate and XPS was used to examine the polyimide and silver fracture surfaces (see Fig. 33). The C(ls) spectra of the silver fracture surface were very similar to those of neat polyamic acid, indicating that imidization was inhibited by interaction of the polyamic acid with the silver substrate. This was evident from the observation of two peaks near... 

In the narrow sense, bis-maleimide resin means the thermosetting resin eom-posed of the bis-maleimide of methylene dianiline (BMI, bis(4-maleimidophenyl)-methane) and methylene dianiline (MDA, bis(4-aminophenyl)methane) (Fig. 1). Beeause of the addition meehanism, the resin is eured without elimination, whieh is a eharacteristic of this resin. Bis-maleimide resin is used as a thermally stable matrix up to 204°C (400 F) whieh typical epoxy resins may not normally be used. However, in spite of having an imide structure, bis-maleimides are classified as being moderately thermally stable resins. The aliphatic structure of the resin is not stable for long periods above 232°C (450°F.) If a highly aromatic thermally stable thermosetting resin is necessary, acetylene end-capped aromatic imide-based oligomers should be used. 

Thionyl imide, HNSO, is a thermally unstable gas, which polymerizes readily. It can be prepared by the reaction of thionyl chloride with ammonia in the gas phase. Organic derivatives RNSO have higher thermal stability, especially when R = Ar. The typical synthesis involves the reaction of a primary amine or, preferably, a silylated amine with thionyl chloride. A recent example is the preparation of FcNSO (Fc = ferrocenyl) shown in Eq. 9.8. In common with other thionylimines, FcNSO readily undergoes SO2 elimination in the presence of a base, e.g., KO Bu, to give the corresponding sulfur diimide FcNSNFc. 

Fig. 6-14 specific modulus = modulus/density. Plastics include use of the heat-resistant TPs such as the polimides, polyamide-imide, and others. Table 6-21 provides data on the thermal properties of RPs. To date at least 80 wt % are glass fiber and about 60 wt% of those are polyester (TS) type RPs. 

Photolysis of chromium alkoxycarbenes with azoarenes produced 1,2- and 1,3-diazetidinones, along with imidates from formal azo metathesis (Eq. 21) [85, 86]. Elegant mechanistic studies [87-89] indicated the primary photoprocess was trans-to-cis isomerization of the azoarene followed by subsequent thermal reaction with the carbene complex. Because of the low yields and mixtures obtained the process is of little synthetic use. 

Sulfur-stabilized ylides underwent photodriven reaction with chromium alkoxy-carbenes to produce 2-acyl vinyl ethers as E/Z mixtures with the E isomer predominating (Table 22) [ 121-123]. The reaction is thought to proceed by nucleophilic attack of the ylide carbon at the chromium carbene carbon followed by elimination of (CO)5CrSMe2. The same reaction occurred thermally, but at a reduced rate. Sulfilimines underwent a similar addition/elimination process to produce imidates or their hydrolysis products (Table 23) [ 124,125]. Again the reaction also proceeded thermally but much more slowly. Less basic sulfilimines having acyl or sulfonyl groups on nitrogen failed to react. 

The thermal imidization of a polyamic acid film (PMDA-ODA or BPDA-ODA) obtained by casting an NMP solution leads to an amorphous polyimide. Two different teams have shown that a polyamic acid solutions in NMP heated at 200°C for a short time (20 min) gives polyimide particles fully cyclized and highly crystalline, as shown by X-ray diffraction and solid 13C NMR spectroscopy.151152 The chemical imidization of the same solution gives only amorphous particles. The difference between the cyclization of a solution and a casted film in the same solvent is intriguing. In the case of the solution, the temperature and the heating time are lower than in the case of the casted film as a consequence, a less organized structure would be expected for the particle. 

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