Bisphenol A bis(phthalic anhydride)

Bisphenol A bis(phthalic anhydride)
Identifiers
3D model (JSmol)
ChEMBL
ChemSpider
ECHA InfoCard 100.048.875
EC Number
  • 253-781-7
UNII
  • InChI=1S/C31H20O8/c1-31(2,17-3-7-19(8-4-17)36-21-11-13-23-25(15-21)29(34)38-27(23)32)18-5-9-20(10-6-18)37-22-12-14-24-26(16-22)30(35)39-28(24)33/h3-16H,1-2H3
    Key: MQAHXEQUBNDFGI-UHFFFAOYSA-N
  • CC(C)(C1=CC=C(C=C1)OC2=CC3=C(C=C2)C(=O)OC3=O)C4=CC=C(C=C4)OC5=CC6=C(C=C5)C(=O)OC6=O
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Bisphenol A bis(phthalic anhydride) (BPADA) is an organic chemical compound and a carboxylic acid anhydride. It consists of a bisphenol A molecule linked to two phthalic anhydride molecules via ether bridges.

BPADA is an important monomer for polyetherimides[1] and polyimides, which are classified as high-performance plastics.[2] Bisphenol A bis(phthalic anhydride) is also the starting material for bisphenol A tetracarboxylic acid, which was recently described under the name "lockdown" as an inhibitor of phosphatases PPM1F and is supposed to prevent the metastasis of tumor cells.[3]

Production

On a laboratory scale, bisphenol A bis(phthalic anhydride) can be synthesized from the disodium salt of bisphenol A (BPA) with a halogen-substituted phthalic anhydride in the 4-position, such as 4-fluorophthalic anhydride.[4][5]

Synthesis of bisphenol-A-bis(phthalic anhydride) with 4-fluorophthalic anhydride
Synthesis of bisphenol-A-bis(phthalic anhydride) with 4-fluorophthalic anhydride

Using the phase transfer catalyst hexaethylguanidinium chloride, BPADA is obtained in 90% yield via a Williamson ether synthesis.

The industrial-scale synthesis of 4,4′-bisphenol-A-bis(phthalic anhydride) starts from N-methylphthalimide (derived from phthalic anhydride and methylamine), followed by nitration (using nitrating acid) to form N-methyl-4-nitrophthalimide (4-NPI).[6] Small quantities of the 3-isomer are also produced, but they can be easily separated.[7] During the reaction of 4-NPI with the sodium salt of bisphenol A, the bis(phthalimide) is formed, which is then hydrolyzed to the tetracarboxylic acid and subsequently dehydrated (e.g. with an acetic acid/acetic anhydride mixture) to yield the dianhydride.[8]

A simplified process converts bisphenol A bisphthalimide to bisphenol A bis(phthalic anhydride) via an imide–anhydride exchange reaction. The reaction occurs in an aqueous phthalic acid solution and is catalyzed by a tertiary amine, such as dimethylbutylamine.[9]

Synthesis of bisphenol-A-bis(phthalic anhydride) with N-methylphthalimide
Synthesis of bisphenol-A-bis(phthalic anhydride) with N-methylphthalimide

Properties

Bisphenol-A-bis(phthalic anhydride) in its pure form is a white crystalline powder that is practically insoluble in water. It dissolves in aprotic dipolar solvents such as dimethylformamide and dimethylacetamide. It also dissolves in alkalis, forming the salt of 4,4′-bisphenol-A-tetracarboxylic acid.

Applications

Due to its difunctional cyclic compounds carboxylic anhydride structure, bisphenol-A-bis(phthalic anhydride)] serves as a hardener for heat-resistant epoxy resins[10][1] and for polyimides.[2] It is also a key molecular building block for polyetherimides (PEI), for example in reactions with phenylenediamines (PPD):

PEI synthesis with bisphenol A bis(phthalic anhydride)
PEI synthesis with bisphenol A bis(phthalic anhydride)

To achieve high molecular weights with improved properties (e.g. color, transparency, and water absorption), high-purity BPADA and precise stoichiometry of the reactants are required, since the polymerization proceeds via polycondensation. Analogous to the formation of hexamethylenediamine adipate in the production of polyamides, the bisphenol A tetracarboxylic acid obtained by hydrolysis of BPADA can react with diamines to form a stoichiometric salt, which polymerizes at approximately 200 °C to yield high-molecular-weight polyimides.[11]

PEI synthesis with bisphenol-A-bis(phthalic anhydride) PEI from AH-analogous salt
PEI synthesis with bisphenol-A-bis(phthalic anhydride) PEI from AH-analogous salt

BPADA imparts advantageous properties to the resulting polymers, such as good solubility in organic solvents (e.g. N-methyl-2-pyrrolidone, dimethylacetamide, chloroform, and tetrahydrofuran),[12] enabling their use in temperature-resistant paints, coatings, and films. Its low water absorption, low dielectric constant, high transparency, and strong adhesion to metal surfaces—especially compared to the standard dianhydride pyromellitic dianhydride (PMDA)—make BPADA particularly suitable for electronic applications.

Bisphenol-A-bis(phthalic anhydride) and its derived polyimides are marketed under the brand name Ultem, such as Ultem 1000 (with the diamine phenylenediamine) and Ultem 5000 (with phenylenediamine), developed by General Electric and now produced and distributed by Saudi Basic Industries Corporation.

A recent publication[3] reports on the in vitro activity of the BPADA hydrolysis product BPADA-tetracarboxylic acid (referred to as "lockdown") as an inhibitor of phosphatases PPM1F, which are often overexpressed in tumor cells. The hydrolysis of the more membrane-permeable precursor BPADA-tetracarboxylic acid tetraethyl ester (designated "LockdownPro"), mediated by endogenous esterases, yields the active compound BPADA-tetracarboxylic acid. This compound is reported to act as an effective PPM1F inhibitor that suppresses tumor cell metastasis. Further studies are required to confirm the in vivo efficacy of such polyvalent crosslinkers and to explore their potential as therapeutic agents for preventing tumor metastasis.

References

  1. 1 2 J.-H. Chang (2020), "Equibiaxially stretchable colorless and transparent polyimides for flexible display substrates", Rec. Adv. Mater. Sci. Eng., vol. 59, pp. 1–9, doi:10.1515/rams-2020-0003
  2. 1 2 A. E. Eichstadt, T. C. Ward, M. D. Bagwell, I. V. Farr, D. L. Dunson, J. E. McGrath (2022), "Synthesis and characterization of amorphous partially aliphatic polyimide copolymers based on bisphenol-A dianhydride", Macromolecules, doi:10.1016/j.chembiol.2022.03.011, PMID 35443151{{citation}}: CS1 maint: multiple names: authors list (link)
  3. 1 2 T.M. Grimm, M. Herbinger, L. Krüger, S. Müller, T.U. Mayer, C.R. Hauck (2022), "Lockdown, a selective small-molecule inhibitor of the integrin phosphatase PPM1F, blocks cancer cell invasion", Cell Chem. Biol., vol. 29, no. 6, pp. 930–946.e9, doi:10.1016/j.chembiol.2022.03.011, PMID 35443151{{citation}}: CS1 maint: multiple names: authors list (link)
  4. ↑ W.T. Schwartz (1990), "A novel route to aryl diether dianhydrides", High Perf. Polym., vol. 2, no. 3, pp. 189–196, doi:10.1177/152483999000200304
  5. ↑ US 20060205958, D.J. Brunelle, J.A. Cella, Q. Ye, K.P. Chan, "Direct dianhydride synthesis", published 2006-9-14, assigned to General Electric Co.
  6. ↑ F.J. Williams, P.E. Donahue (1978), "Nitration of N-alkylphthalimides", J. Org. Chem., vol. 43, no. 8, pp. 1608–1610, doi:10.1021/jo00402a036
  7. ↑ US 4048190, D.S. Johnson, F.J. Williams, III, "Preparation of bisphenol-A bisimides", published 1977-9-13, assigned to General Electric Co.
  8. ↑ US 3879428, D.R. Heath, T. Takekoshi, "Method for making aromatic bis(ether anhydride)s", published 1975-4-22, assigned to General Electric Co.
  9. ↑ US 4584388, J.L. Webb, "Method and composition for preparing aromatic polycarboxylic acids and their anhydrides from polycarboximides", published 1986-4-22, assigned to General Electric Co.
  10. ↑ "Achieving high heat epoxy formulations using BISDA". Version 1.0. SABIC’s Specialties Business Thermosets & Additives. 2019. Retrieved 2022-04-23.
  11. ↑ Kevin J. Bigham (July 2007). "RESINATE No.7: Focus on Polyimides" (PDF). Zeus Industrial Products, Inc. Retrieved 2022-04-23.
  12. ↑ "Building polyimide varnishes and films using high purity BPADA". SD1100P Powder Technical Bulletin. SABIC’s Specialties Business, Thermosets & Additives. 2021. Retrieved 2022-04-23.
This page is issued from Wikipedia. The text is available under Creative Commons Attribution-Share Alike 4.0 unless otherwise noted. Additional terms may apply for the media files.