Synthesis of polyimides from 2,5‐di(carboxymethyl)terephthalic dianhydride and diamines

Ueda, Mitsuru; Takahashi, Masayoshi; Hishiki, S.; Imai, Yoshio

doi:10.1002/pol.1979.170170818

Cited by 7 publications

(2 citation statements)

References 5 publications

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“…The autocatalyzed alcoholysis of PMDA ( 1 ) in excess alcohol has been shown to give the expected mixture of para ( 3 ) and meta ( 4 ) diesters (Scheme ), ,– separated by chromatography or fractional crystallization.…”

Section: Resultsmentioning

confidence: 99%

Esters of Pyromellitic Acid. Part I. Esters of Achiral Alcohols: Regioselective Synthesis of Partial and Mixed Pyromellitate Esters, Mechanism of Transesterification in the Quantitative Esterification of the Pyromellitate System Using Orthoformate Esters, and a Facile Synthesis of the Ortho Pyromellitate Diester Substitution Pattern

Paine

2008

J. Org. Chem.

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Mild conditions and reversible anhydride formation allow a relative differentiation to be made of the four equivalent carbonyl groups of pyromellitic dianhydride (PMDA, benzene-1,2,4,5-tetracarboxylic dianhydride) in esterification, leading to regioselective methods to generate a wide range of partially or totally esterified products or products bearing differing esterifying groups at the different positions. Pyromellitate monoester anhydrides form efficiently in dichloromethane/triethylamine from 1 equiv of the alcohol. Under the same conditions, two different alcohols can be made to react sequentially. With 2 equiv of an alcohol, the usual mixture of meta and para diesters is obtained, separated by crystallization from HOAc. Meta and para dibenzyl pyromellitates served as regiospecific sources of other diesters, by further esterification followed by hydrogenolysis. Refluxing orthoformate triesters were found to effect quantitative esterification of the pyromellitate system under autocatalytic conditions; minor ester exchange with pre-existing esters (0-5% of total product) was ascribed to reversible anhydride formation. For general esterification with alcohols, partial ester acid chlorides were obtained using oxalyl chloride. Pyromellitate triesters afforded the ortho diester anhydrides upon distillation, thereby providing facile entry into the mostly novel ortho substitution pattern in this system. The requisite triesters were prepared by selective saponification or by the prior incorporation of one benzyl ester substituent, which could be removed by catalytic hydrogenolysis. The various benzyl esters of pyromellitates hydrogenolyzed smoothly to release the carboxylic acid groups without disturbance of pyromellitate aromaticity.

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Section: Resultsmentioning

confidence: 99%

Esters of Pyromellitic Acid. Part I. Esters of Achiral Alcohols: Regioselective Synthesis of Partial and Mixed Pyromellitate Esters, Mechanism of Transesterification in the Quantitative Esterification of the Pyromellitate System Using Orthoformate Esters, and a Facile Synthesis of the Ortho Pyromellitate Diester Substitution Pattern

Paine

2008

J. Org. Chem.

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“…Polyimides prepared with different proportions of m-phenylenediamine, p-phenylenediamine, or p,p'-diaminobiphenyl, with pyromellitic dianhydride has integral procedral decomposition temperatures ranging from 620 to 651 °C in air and 643 to 754 °C in N2 (192). Polyimides derived from 2,5-di(carboxymethyl)-terephthalic dianhydride and diamines decomposed from 370 to 445 °C in air and 420 to 470 °C in N2 (186). Hydroxyl-containing polyamides, prepared by ring-opening polyaddition of 3,3'-disubstituted bis-d-propiolactone with diamines, melted and decomposed around 200 °C (187).…”

Section: Differential Thermal Analysis-dynamic Scanning Calorimetrymentioning

confidence: 99%

Thermal analysis

Murphy¹

1980

Anal. Chem.

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Polyimides from dianhydrides and bis(p‐aminophenyl) alkane diamines. I

Ghatge¹,

Shinde²,

Mulik³

1984

J. Polym. Sci. Polym. Chem. Ed.

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SynopsisPolyimides were synthesized from pyromellitic dianhydride (PMDA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA), and three different diamines with the following general structure: R where R is ethyl, propyl, or isobutyl. The poly(amic acids) obtained had inherent viscosities ranging from 0.30 to 0.93 and were thermally/chemically converted to polyimides. The thermal stability of the polyimides was evaluated by using dynamic thermogravimetric analysis in air. Physical and thermal properties of these polyimides were compared with that obtained by reacting 2,2-bis(4aminophenyI) propane and PMDA/BTDA. 1. 2,2-bis(4-aminophenyl) propane (PRDA) 2. 2,2-bis(4-aminophenyl) butane (BUDA) 3. 2,2-bis(4-aminophenyl) pentane (PEDA) 4. 2,2-bis(4-aminophenyl)-4-methylpentane (MPDA) Although the reaction of PRDA with PMDA has been reported previously, the polymer was again synthesized under identical conditions for the comparative study.

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Synthesis of polyimides from 2,5‐di(carboxymethyl)terephthalic dianhydride and diamines

Cited by 7 publications

References 5 publications

Thermal analysis

Polyimides from dianhydrides and bis(p‐aminophenyl) alkane diamines. I

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