Biphenyl-3,3 ,4,4 -tetracarboxylic dianhydride

Generally, synthesis of dianhydrides is somewhat more complex than that of diamines and until recent time pyromellitic dianhydride (PMDA) and benzophenone-3,3, 4,4 -tetracarboxylic dianhydride (BTDA) had been the only commercially produced aromatic dianhydrides. Some of the significant commercial products developed recently, are Upilex by UBE Ind. and Ultem by General Electric. The former is based on biphenyl-3,3, 4,4 -tetracarboxylic dianhydride (BPDA) and the latter on 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride or bisphenol A dianhydride (BPA-DA). BPDA is produced by oxidative coupling of inexpensive phthalic acid esters in the presence of palladium catalyst [23, 24]. 

Biphenyl-2,3,3, 4 -tetracarboxylic dianhydride, 476 Biphenyl-3,3, 4,4 -tetracarboxylic dianhydride, 476 Biphenyltetracarboxylic dianhydride, 476... 

Biaryl derivatives bearing reactive groups have become increasingly important in industry. Uses for this class of compounds are constantly being developed in the production of high performance polymers. Materials such as 3,3, 4,4 -biphenyl-tetracarboxylic dianhydride 1 and 4,4 -biphenol 2 are monomers employed in the manufacture of high performance polyimides or polyesters. Applications for this family of molecules have also been found both in the dye industry and in the pharmaceutical industry. 

Starting materials and solvents were purchased from Aldrich Chemical Co. acetonitrile (ACN), N,N-dimethylformamide (DMF), and N-methyl-2-pyrrolidone (NMP) were obtained anhydrous in Sure/Seal bottles and used as received. The polyamic acid of PMDA-ODA (2545 Pyralin) was supplied by DuPont. The soluble polyimide XU-218, derived from 3,3, 4,4 -benzophenone tetracarboxylic dianhydride (BTDA) and diamino-1,1,3-trimethyl-3-phenylindan isomers (DAPI) was purchased from Ciba-Geigy Corp. The acetylene terminated imide oligomer powder (Thermid MC-600) derived from BTDA, aminophenylacetylene, and 1,3-bis (2-aminophenoxy) benzene (APB) was obtained from National Starch and Chemical Company. Kapton Type II (PMDA-ODA) films were obtained from DuPont Co., Apical polyimide films were obtained from Allied Corp., and Upilex Type-S and Type-R polyimide films derived from 3,3, 4,4 -biphenyl tetracarboxylic dianhydride (BPDA) plus p-phenylenediamine (PDA) and ODA, respectively were obtained from ICI Americas Inc. 

C22H14N206 polyamidocarboxylic acid based on 3,3, 4,4 -biphenyl-tetracarboxylic dianhydride and para-phenylene diamine 182... 

Diamino-benzanilide (DABA) Wakayama Seika 3,3 4,4 -Biphenyl tetracarboxylic dianhydride (BPDA) Chriskev, Mitsubishi, Ube... 

PETI-5 3,4 -Oxydianiline, 1,3-bis (3-amino phenoxy benzene) and 3,3, 4,4 -biphenyl tetracarboxylic dianhydride encapped with 4-phenylethynyl pthalic anhydride Phenyl ethynyl 270/250 [141-143]... 

Poly(amide imide) of biphenyltetracaiboxylic dianhydride PoIy(3,3, 4,4 -benzophene tetracarboxylic dianl dride) Poly(3,3, 4,4 -biphenyl tetracarboxylic dianhydride) Poly(2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane... 

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). 

Benzophenone, 4,4 -dihydroxy-. See 4,4 -Dihydroxybenzophenone Benzophenone, 2-hydroxy-4-(octyloxy)-. See Benzophenone-12 2-Benzophenone, methyl-. See 2-M ethyl benzophenone p-Benzophenone, methyl-. See 4-M ethyl benzophenone Benzophenone, 4-phenyl-. See p-Phenylbenzophenone 4-Benzoyl biphenyl Benzophenone tetracarboxylate dianhydride 3,3, 4,4 -Benzophenonetetracarboxylate dianhydride. See 3,3, 4,4 -Benzophenone tetracarboxylic dianhydride... 

Sulfonated polyimides (sPI) are another type of ionomers that have been prepared [5] by copolymerization of 4,4 -diamino-biphenyl 2,2 -disulphonic acid (BDSA), 4,4 -oxydianiline (ODA), and naphtalenic or phthalic anhydrides. Polyimide structures based on six-membered rings derived from naphtalenics anhydrides, such as 1,4,5,8-naphtalene tetracarboxylic dianhydride (NTDA), shown in Fig. 6.8, are more hydrolitically stable than the five-membered rings basedoxy-diphthalic anhydrides (ODPA). 

Neither polyimides derived from 1,2,4,5-benzenetetracarboxylic dianhydride (PMDA) nor from biphenyl tetracarboxylic anhydride with aliphatic spacers have yielded a liquid crystalline phase. The need for an extraring to obtain meso-genic properties was evident. Inoue et al. reported the existence of mesophase in a series of polyimides synthesized from the nylon-salt-type terphenyl tetracarboxylic anhydride with aliphatic diamines (Structure 4) [53-55]. 

Materials The materials in this work includ< a lyotropic polyamide (PBTA) composed of terephthaloyl dichloride and 2,2 -dimethyI-4,4-diamino-biphenyl two amorphous polyimides respectively con sting of 3,3 4,4-benzophenone tetracarboxylic dianhydride (BTDA) and 2,3,5,6-tetrameth -p-phenylene diamine (TMPD), as well as 4,4 -(hexafluoroisopropylidene)>bis(phthalic anhydride) (6FDA) and 2,2-dimethyl-4,4-diamino-biphenyl (DMDB) and the block copolymers composed of PBTA and those two polyimides with various compositions. Ilie PBTA/PI block copolymers and the corresponding homopolymers were prepared according to our previous work(79). 

All these dianhydrides should have a very high reactivity, because of the lower values of lumo for both the dianhydride and the monoamide. In fact, hexafluoroisopropyliden 4,4 -diphthalic anhydride should be only slightly less reactive than benzophenone tetracarboxylic dianhydride, and 2,3,6,7-naphthalene tetracarboxylic dianhydride should be very similar to biphenyl dianhydride. But if the reaction is controlled by the monoamide, as we have postulated, the most reactive dianhydride should be 1,4,5,8-naphthalene tetracarboxylic dianhydride, because lumo is almost the same than for pyromellitic dianhydride, but lumo monoamide is lower than lumo monoamide of the pyromellitic (—2.33 versus — 2.18eV). 

Biphenyl tetracarboxylic add dianhydride/phenylene diamine (BPDA-PDA) polyamic acid, 14.5% solids in N-methylpyrrolidone (NMP), TEF SOB, 60%... 

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. ... 

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