Tetracarboxylic acid dianhydrides

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. ... 

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)... 

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). 

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. 

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

Fully imidized soluble polyimides have ben prepared using monomers derived from diphenylindane and aromatic dianhydrides. Technical polymers (XU218, for instance), prepared from 1,1,3-trimethyl-diaminophenylindane and benzophenone-tetracarboxylic acid dianhydride, have been marketed over the last decade. Despite the partially aliphatic nature of polyimides containing the indane group, they show considerable retention of the thermal stability, with Tg values over 300 °C [107-110]. 

From BPA/DC and pyromellitic dianhydride, linear polyimidocarbamates were synthesized [27-29]. For the same purpose, various dicyanates and tetracarboxylic acid dianhydrides were used [29-31]. If one of the starting monomers has a functionality higher than 2, crosslinked polymers are obtained,... 

Benzoquinone tetracarboxylic acid dianhydride (BTDA) has been found to provide epoxy adhesives with excellent high-temperature properties, in both the short and long terms. The formulation described in Table 12.12 provides good resistance to 260°C. This two-part adhesive can be cured 2 h at 200°C. The disadvantage of BTDA is that relatively high cure temperatures are required that result in a high degree of internal stress within the bond line. 

A new quality in ladder polymer synthesis via multifunctional polycondensation was reached in the late 1960s when poly(benzimidazobenzo-phenanthroline) (BBL) 12 was prepared by Arnold and van Deusen [21 -24]. The polymer was synthesized from naphthalene-l,4,5,8-tetracarboxylic acid dianhydride (11) and 1,2,4,5-tetraaminobenzene (la) in strong acidic media (polyphosphoric acid, sulfuric acid). BBL is completely soluble in concentratal sulfuric acid or methanesulfonic add and is processible into durable films and... 

The polyimide is prepared from 1,5 naphthlene diamine (1,5 ND) and 3,3, 4,4 diphenylhexafluoroisopropylidene tetracarboxylic acid dianhydride (6F). A polyamide acid is obtained initially and this is cyclized to give the polyimide. Because polyimides are derivatives of polyamides, polyimides are often included in reviews of aromatic polyamides. Another reason polyimides are included in this paper is that they illustrate the role of Structure Level II on gas transport properties in a straightforward manner. 

IR spectroscopy may be used to follow two reactions occurring in polyimides exposed to high temperatures and humidities hydrolysis of the imide linkages and hydrolysis of residual anhydride end groups. The hydrolytic susceptibilities of several polyimides were measured at 90°C/95% R.H. Polymers based on benzophenone tetracarboxylic acid dianhydride (with either oxydianiline or m-phenylene diamine) appeared to undergo rather rapid hydrolysis initially, but the reaction had essentially halted by the time the measured imide content had decreased by 5-6%. Polymers based on 3,3 ,4,4 -biphenyl tetracarboxylic acid dianhydride (with p-phenylene diamine) and pyromellitic dianhydride (with oxydianiline) showed no significant imide hydrolysis. In all the polymers, the anhydride was hydrolyzed quite readily. 

The polyamic acids were prepared in these laboratories using modifications of a standard preparation (7). Benzophenone tetracarboxylic acid dianhydride (BTDA), benzenetetracarboxylic acid dianhydride (pyromellitic dianhydride PMDA), oxydianiline (ODA), 1,4-phenylenediamine (PDA) and 1,3-phenylenediamine (MPDA) were all obtained from Aldrich Chemical Co. The S -biphenyl tetracarboxylic acid dianhydride (BPDA) was obtained from Ube Chemical Company. The polyamic acids were prepared in N-methylpyrrolidinone (BTDA-ODA, BTDA-MPDA and BTDA with a 1 1 molar ratio of MPDA and ODA) or dimethyl acetamide (BPDA-PDA and PMDA-ODA). 

The fact that all bis(naphthalic anhydrides) display lower reactivity than naphthalene-1,4,5,8-tetracarboxylic acid dianhydride, has predetermined an expedient synthesis of their polyheteroarylenes. It involves catalytic processes which find wide application in polycondensation and polycyclocondensation reactions [154, 155]. 

In contrast to a more rigid polymer derived from naphthalene-1,4,5,8-tetracarboxylic acid dianhydride precipitating from m-cresol at this concentration, the obtained polyimides retained solubility in m-cresol up to a concentra-... 

In contrast, polynaphthoylenebenziniidazote based on 2,2-bis(3,4-diaminophenyl) hexafluoropropane are soluble not only in H2SO4, m-cresol and a tetrachloroethane-phenol mixture (3 1) (this is characteristic for polymers derived from bis(o-phenylenediamine) and naphthalene-l,4,5,8-tetracarboxylic acid dianhydride [183, 184]) but also in N-MP (N-methylpyrolidane). An enhanced solubility of polynaphthoyleiKbenzimidazoles of this series is explained not only by the introduction of a hinge group between naphthalic anhydride moieties, but also by low viscosity characteristics of the systems caused by low basicity of 2,2-bis(3,4-diaminophenyl)hexafluoropropane [185],... 

Naphthalene-l, 4,5,8-tetracarboxylic acid dianhydride 118, 137, 138, 140, 146, 147 2,6-Naphthalenedicarboxylic acid 196 Nonlinear optical polymers 36... 

Synthesis of polyimides directly from perylene-3,4,9,10-tetracarboxylic acid dianhydride (DPTA) [4, 5] using diamines as the nucleophilic comonomers which leads to improved solubility for the target polymers. 

It was shown that soluble PPI can be synthesised directly from DPTA and series of aromatic diamines containing flexible units, namely 2,2-bis[4-(3-aminophenoxy)phenyl]propane and 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoro-propane were reported (Scheme 1.2) [5]. Previously these diamines were used successfully in the synthesis of soluble polyimides starting from naphthalene-1,4,5,8-tetracarboxylic acid dianhydride [14]. 

Polyimides Based on Naphthalene-1,4,5,8-Tetracarboxylic Acid Dianhydride... 

Another class of polyimides that are characterised by a higher chain flexibility, when compared to PPI, are based on naphthalene-l,4,5,8-tetracarboxylic acid dianhydride (DNTA). These polymers are of considerable interest due to their high heat resistance and thermal stability and due to easy accessibility of the starting monomers. DNTA is a widely available dianhydride showing the highest electrophilic reactivity among bisfnaphthalene-tetracarboxylic anhydrides [18, 19]. 

Not all attempts at formations of ladder polymers yielded completely cyclized fused ring structures. For instance, an attempt to form a polymer from tetraaminonaphthalene with naphthalene tetracarboxylic acid dianhydride failed to yield complete cyclizations [222]. 

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