Chemical imidation

Tsuchiya, T., Kurita, J. and Takayama, K. (1980) Studies on diazepines. XIII. Photochemical behaviour of pyrazine, pyrimidine, and pyridazine N-imides. Chemical el Pharmaceutical Bulletin, 28 (9), 2676-2681. 

Polyamide-imide chemical resistance to solvents is high. Polyamide-imide is resistant to aliphatic and aromatic hydrocarbons, solvents, acids, and exhibits limited resistance to weak bases. Table A.30 Appendix. 

To avoid these problems, refiners commonly use additives called detergents" (Hall et al., 1976), (Bert et al., 1983). These are in reality surfactants made from molecules having hydrocarbon chains long enough to ensure their solubility in the fuel and a polar group that enables them to be absorbed on the walls and prevent deposits from sticking. The most effective chemical structures are succinimides, imides, and fatty acid amines. The required dosages are between 500 and 1000 ppm of active material. 

Heating Kemp s acid with appropriate aromatic diamines yields bis-imides with two convergently oriented carboxylic acid groups on the edges of a hydrophobic pocket. Dozens of interesting molecular complexes have been obtained from such compounds and can be traced in the Journal of the American Chemical Society under the authorship of J. Rebek, Jr., (1985 and later e.g. T. Tjivikua, 1990 B). 

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. 

LARC-TPI is a linear thermoplastic PI which can be processed ia the imide form to produce large-area, void-free adhesive bonds. Mitsui Toatsu Chemicals, Inc., has obtained Hcense to produce this product commercially for appHcations such as adhesives, films, mol ding compounds, etc. These are thermooxidatively stable and show essentially no loss ia weight at 300°C ia air. Weight loss does not exceed 2—3% after isothermal aging ia air at 300°C for 550 h. 

Reactions. Although carbapenems are extremely sensitive to many reaction conditions, a wide variety of chemical modifications have been carried out. Many derivatives of the amino, hydroxy, and carboxy group of thienamycin (2) have been prepared primarily to study stmcture—activity relationships (24). The most interesting class of A/-derivatives are the amidines which are usually obtained in good yield by reaction of thienamycin with an imidate ester at pH 8.3. Introduction of this basic but less nucleophilic moiety maintains or improves the potency of the natural material while greatiy increasing the chemical stabiUty. Thus /V-formimidoyl thienamycin [64221-86-9] (MK 0787) (18), C 2H yN204S, (25) was chosen for clinical evaluation and... 

The Michael addition of nucleophiles to the carbon—carbon double bond of maleimide has been exploited ia the synthesis of a variety of linear polymers through reaction of bismaleimide with bisthiols (39). This method has been used to synthesize ethynyl-terminated imidothioether from the reaction of 4,4 -dimercaptodiphenyl ether [17527-79-6] and A/-(3-ethynylphenyl)maleimide (40). The chemical stmcture of this Michael addition imide thermoset is as follows ... 

Polyamide Imides. Polyamide imides (PAIs) are formed from the condensation of trimellitic anhydride and aromatic diamines (33). The polymer is called amide—imide because the polymer chain comprises amide linkages alternating with imide linkages, with the general chemical stmcture ... 

Post-Curing. Whenever production techniques or economics permit, it is recommended that compounds based on terpolymer grades be post-cured. Relatively short press cures can be continued with an oven cure in order to develop full physical properties and maximum resistance to compression set. Various combinations of time and temperature may be used, but a cycle of 4 h at 175°C is the most common. The post-cure increases modulus, gready improves compresson set performance, and stabilizes the initial stress/strain properties, as chemically the polymer goes from an amide formation to a more stable imide formation. Peroxide-cured dipolymer compounds need not be post-cured. 

If trimellitic anhydride is used instead of pyromellitic dianhydride in the reaction illustrated in Figure 18.35 then a polyamide-imide is formed (Figure 18.37). The Torlon materials produced by Amoco Chemicals are of this type. 

The ethyl cyanoacetate and methyl ethyl ketone were Eastman Kodak Company white label grade chemicals and were used without further purification. Commercial absolute ethanol was found to give a slightly better yield of the ammonium salt of the imide. 

Materials and additives that are chemically basic in nature have a detrimental effect on the curing of cationic-initiated epoxy systems. These substances can either stop the curing mechanism completely or produce under-cured polymers. Therefore such additives as amines or imides that are known to be adhesion promoters cannot be used in the EB-curable epoxy adhesive formulations. 

Fig. 3.1 NMR chemical shifts for NH groups in cyclic sulfur imides...

Photosensitive functions are in many cases also heat sensitive, so the preparation of photosensitive polyimides needs smooth conditions for the condensations and imidization reactions. Some chemical reactants, which can be used for polyamide preparation, have been patented for the synthesis of polyimides and polyimide precursors. For example, chemical imidization takes place at room temperature by using phosphonic derivative of a thiabenzothiazoline.102 A mixture of N -hydroxybenzotriazole and dicyclohexylcarbodiimide allows the room temperature condensation of diacid di(photosensitive) ester with a diamine.103 Dimethyl-2-chloro-imidazolinium chloride (Fig. 5.25) has been patented for the cyclization of a maleamic acid in toluene at 90°C.104 The chemistry of imidazolide has been recently investigated for the synthesis of polyimide precursor.105 As shown in Fig. 5.26, a secondary amine reacts with a dianhydride giving meta- and para-diamide diacid. The carbonyldiimidazole... 

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. 

Development of several new siloxane-imide copolymers for commercial applications have also been reported by Lee 181) and Berger58). Although no information was given in terms of the chemical compositions of these materials, most of these polymers were reported to be processable by solution or melt processing techniques, most probably due to their high siloxane contents. However, due to the presence of low (—20 to —120 °C) and high (>230 °C) temperature Tg s, it was clear that multiphase copolymers have been synthesized. Molecular weights and thermal stabilities, etc, were not reported. 

SCHEME 2.14 Uncatalyzed, base-catalyzed, and reductive generation of QMs tethered to a naphthalene imide core, through the TSs TS-NI, TS-NI, and TS-NI, respectively [bond lengths are in A data in parentheses are for full R(U)B3LYP/6-31 +G(d,p) optimization in aqueous solution] (reproduced from Ref. [47] with permission from American Chemical Society). (See the color version of this scheme in Color Plates section.)... 

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