Dianhydrides, acid

Pigment Orange 43 [4424-06-0] 71105 Perinone condensation of naphthalene-1,4,5,8-tetracarboxyhc acid dianhydride with o-phenylenediamine, and separation of trans isomer... 

Pigment Red 179 [5521-31-3] 71130 Perylene imidation of perylene 1,6,7,12-tetra-carboxyhc acid dianhydride with methylamine... 

Rather similar are the 5.5-dimethylhydantoin derivatives shown in Figure 26.18 (b, e). These resins are said to eonfer improved weathering resistance but also exhibit higher water absorption. Another trifunctional material is p-glycidyl-oxy-A,A/-diglycidylaniline. This has been recommended for adhesive systems in conjunction with benzophenonetetracarboxylic acid dianhydride, which is a room temperature curing agent in this case. 

Other examples of this synthetic strategy are known for example, a recent zirconium polymer by Illingsworth and Burke (8), who joined amine side groups of a zirconium bis(quadridentate Schiff-base) with an acid dianhydride to give amide linkages. Once again, caution is necesary, as Jones and Power (2) learned when they attempted to link metal bisO-diketonates) with sulfur halides that is, they obtained insoluble metal sulfides because the p-diketone complexes which they used were fairly labile and the insolubility drove the reactions to completion in the wrong direction. 

The polyamic acid (Fig. 3.7) precursor was prepared by adding stoichiometric amounts of3,3,4,4-benzophenonetetracarboxylic acid dianhydride (BTDA) anddiami-nodiphenylsulfone (DDS). The solution in NMP was then submitted to either thermal or MW activation with accurate monitoring of the temperature (Scheme 3.14). 

Polyimides derived from 3,3, 4,4 -benzophenone tetracarboxylic acid dianhydride (BTDA), I, and 3,3 -diaminobenzophenone (m,m -DABP), IIA, 4,4 -diaminobenzophenone (p,p -DABP), IIB, or 4,4 -oxydianiline, IIC, (and to which have been added numerous metal compounds) have been prepared. The synthetic procedure em-... 

Dibenzothiophene acts as a 7r-electron donor and readily forms complexes with known electron acceptors. In such cases the electronic spectrum of a solution of the two compounds shows a new absorption band, usually in the visible region. The order of donor strengths of several o,o -bridged biphenyls has been estimated from their respective charge-transfer spectra and found to be carbazole > fluorene > dibenzothiophene >dibenzofuran. Dibenzothiophene forms complexes with tetracy-anoethylene, various polynitro derivatives of fluorenone, > naphthalene-1,4,5,8-tetracarboxylic acid dianhydride, and tetra-methylmic acid. ... 

Synthesis of PIQ. Very high heat resistance is required in order for a polymer film to be used as an insulator. This is because several heat treatments over 400 C are necessary in LSI interconnection and assembly processes. An aromatic polyimide (I), a reaction product of aromatic diamine and acid dianhydride, is one of the most heat resistant polymeric materials ... 

Analyses of Water Content. The water content of the PIQ starting materials was analyzed. The water content of amines was measured using a DuPont 321A moisture meter and those of the solvents were measured by Karl Fischer s reagent method. The water content of acid dianhydrides was measured by titrating the free acid. 

The water content in the starting materials was measured as follows. The water content of amines and solvents were measured using the DuPont 321A moisture meter and Karl Fischer s reagent methods, respectively. Since the water contained in acid dianhydride is considered to convert it to free acid. 

The results are shown in Table 1. The table shows that the greatest part of the water in the starting materials is present in the acid dianhydrides. This was verified by experimental results. That is, water content increases with time and that increase strongly depends on ambient humidity, as shown in Figure 5. Therefore, it is very important to keep the materials dry. 

In order to reduce the water content, dehydration of the starting materials were carried out as follows. Acid dianhydrides were recrystallized in acetic anhydride and dried by infrared lamp. Amines were recrystallized in butyl alcohol and dried. Solvents were distilled under reduced pressure. The water content of the dehydrated materials is also given in Table 1. A remarkable reduction in water content was achieved. 

The influence of water on heat resistance of cured PIQ film was examined as follows. PIQ prepolymer solutions were synthesized using moist acid dianhydrides and PIQ films were formed from these solutions. Next, heat treatment was carried out on the films at 450 C in air and their weight residues were measured. The results are shown in Figure 6. It was found that even a small amount of water greatly decreased the heat resistance of PIQ. 

The influence of water on heat resistance is considered to be as follows. Moist acid dianhydrides include free acid, as mentioned before. When PIQ is thermally cured, free acids are converted into corresponding dianhydride monomers and evaporate. 

Ethane-tetracarboxylic Acid Dianhydride, [3,7-Dioxa-2,4,6,8 tetra-oxo-bicyclo(3,3,0)-octane], mw 170.1, OB to COg —66%, cryst, dec over 150°. It was first prepd in 1920 by heating the acid in a six-fold excess of acetic anhydride at 70—75°, then in 1923 by treating the acid with AcCl and heat, or by treating with oxalyl chloride, the acid or the tetra-silver salt of the acid (Ref 6)... 

Antireflective polyester compositions for photoresists consisting of butanetetra-carboxylic acid dianhydride and styrene glycol, (I), and tetramethylglycol uril,... 

Figure 14.5. Two-step acylation reactions that generate poly(amic acid) from diamine and tetra-carboxylic acid dianhydride (reproduced by permission of the American Chemical Society, from Ando...

This book reviews some of the results of investigations of chemical conversions of chloral and TNT to new aromatic di(poly)amines and aromatic tetracarboxylic acid dianhydrides useful for the preparation of new polyimides combining good thermal, mechanical and electrical properties with improved processability. 

Along with new aromatic diamines and tetramines based on chloral and its derivatives, new aromatic tetracarboxylic acid dianhydrides were developed. These products were prepared by the interaction of bis-phenols - chloral derivatives - with two-fold molar amounts of nitrophthalimides followed by transformation of bis-phthalimides, containing two ether bonds, into the corresponding aromatic tetracarboxylic acid dianhydrides [30] (Scheme 2.13). 

Polyimides with better viscosity characteristics have been obtained from 3,3 -diamino-4,4 -bis(dimethylamino)-benzophenone and different aromatic tetracarboxylic acid dianhydrides [21] (Scheme 3.4). 

A number of conventional synthetic procedures have been used to prepare polyimides [1—4]. These are the low-temperature condensation of 3,5-diaminoanisole with acid dianhydrides, conducted in amide solvents, followed by thermal imidisation of the poly(o-carboxy)-amides (PCA) formed low temperature condensation of 3,5-diaminoanisole with acid dianhydrides, conducted in amide solvents, followed by catalytic imidisation of PCA using a 1 1 pyridine-acetic anhydride complex as a catalyst and high temperature (160-180 °C) condensation of 3,5-diaminoanisole with acid dianhydrides, conducted in m-cresol, using quinoline, isoquinoline or benzoic acid as a catalyst. 

The reaction between 3,5-diaminoanisole and acid dianhydrides in amide solvents (above all N-methyl-2-pyrrolidone, NMP) was conducted at room temperature. The process occurred in a homogeneous system and led to PCA with relatively high, reduced viscosities of solution (Table 5.1). 

Up to the decomposition temperature, polypyromelliteimide based on 3,5-diaminoanisole does not soften. The softening points of polyimides prepared from benzophenonetetracarboxylic and diphenyloxidetetracarboxylic acid dianhydrides are 300 and 310 °C, respectively, (Table 5.1). 

Hence, heat resistance of the synthesised polyimides decreases with variation of the structure of the acid dianhydride fragment in the following order ... 

None of the polyimides synthesised dissolve in amide solvents, including NMP. Moreover, the polyimide prepared from 3,5-diaminoanisole and diphenyloxidetetracarboxylic acid dianhydride is soluble in OT-cresol and a mixed trichloroethane/phenol (3 1) solvent, whereas the polypyromelliteimide and polyimide based on benzophenonetetracarboxylic acid dianhydride do not dissolve in these phenolic solvents. 

The fact that the polyimide based on diphenyloxidetetracarboxylic acid dianhydride is soluble in phenolic solvents enabled the authors to prepare (using solutions of this polymer in w-cresol and mixed trichloroethane/phenol solvent) almost colourless films showing (at 25 °C) a tensile strength of 114 MPa and a 9% elongation at break. 

New representatives of such polyimides were prepared from TNT-based perfluoro-substituted m-phenylenediamines and different aromatic tetracarboxylic acid dianhydrides [9-12] in accordance with Scheme 5.2. Reactions were carried out in w-cresol using isoquinoline as catalyst. The reaction temperature was 160 °C and the reaction time 5 hours. 

Polyimides based on l-amino-3-phenoxy-5-(4-aminophenoxy)-benzene and snch dianhydrides as dianhydride of diphenyloxide-3,3 4,4 -tetracarboxylic acid, dianhydride A and dianhydride 6F are soluble in NMP, dimethylformamide (DMF), w-cresol, THF and chloroform. The polyimide based on benzophenone-3,3, 4,4 -tetracarboxylic acid dianhydride is partially soluble in w-cresol and NMP it is insoluble in chloroform, THF and DMF. Polypyromellitimide is insoluble in all the solvents tested. 

Polyimides based on 3,5-diaminodiphenylsulfide demonstrate that solubility in organic solvents strongly depends on the nature of the dianhydride used polymers based on dianhydride 6F and dianhydride A are soluble in NMP, chloroform and acetone polyimides based on diphenyloxide-3,3, 4,4 -tetracarboxylic and benzophenone-3,3, 4,4 -tetracarboxylic acid dianhydrides are soluble in NMP only. Polyimides demonstrate high aired NMP (0.79-1.20 dl/g) and moderate (210-250 °C) Tg values combined with high (400-460 °C) T egr-... 

Interaction of 2-niethyl-3,5-diaminodiphenylsulfide with aromatic tetracarboxylic acid dianhydrides was carried out in accordance with Scheme 5.6. Synthesis of the polyimides was carried out using two general procedures ... 

Room temperature interaction of the diamines and tetracarboxylic acid dianhydrides, in NMP, leading to the formation of poly(o-carboxy)-amides followed by catalytic imidisation of these polymers with pyridine-acetic anhydride complex. 

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