Synthesis of the Ultem series polyetherimides

Polyetherimides (PEIs) are a class of structural polymers with the most successful combination of such essential properties for practical applications as high heat resistance, thermal stability, ultimate tensile strength, elastic modulus, good dielectric properties, and high chemical and radiation resistance. However, along with these advantages, PEIs are compounds with high softening and melting points, which complicates their processing into products. In recent decades, specialists have found numerous ways to decrease the glass transition temperature by increasing the flexibility of the main polymer chain. To this end, functional groups with a higher degree of rotation, such as isopropylidene, hexafluoroisopropylidene, 1,2-dichloroethylene, and other substituents, are introduced into the main polymer chain. Polyetherimide, whose precursors are 3(4)-nitrophthalic anhydride, m-phenylenediamine, and bisphenol A, was first produced by General Electric under the Ultem brand name and is currently believed to be one of the best-known engineering thermoplastics. In particular, two synthetic methods can be used to obtain such polyetherimides. The first technique uses a cyclization of poly(amidocarboxylic acid), which is obtained by the polycondensation of dianhydride of 2,2-bis-[4-(3,4-dicarboxyphenoxy)phenyl]propane and m-phenylenediamine. The second technique uses the polynitro substitution of 1,3-bis[N-(3-nitrophthalimido)]benzene and the dynatrium salt of bisphenol A. To date, the Russian scientific literature lacks reviews with detailed descriptions of known methods for the preparation of Ultem series polyetherimides. The present review generalizes and systematizes the available literature data regarding the synthesis of the Ultem series PEIs. In addition, this study describes preparation methods of soluble thermoplastic polyetherimides of this series, available synthesis methods of initial monomers with reaction yields, and physical characteristics of such polymers.

1. Borodulin A.S., Kalinnikov A.N., Muzyka S.S., Tereshkov A.G. Polyetherimides for creating heatresistant polymer composite materials with changes in physical and mechanical properties. Vestnik Belgorodskogo gosudarstvennogo tekhnologicheskogo universiteta im. V.G. Shukhova = Bulletin of BSTU Named after V.G. Shukhov. 2019;(11):94-100. (In Russian). https://doi.org/10.34031/2071-7318-2019-4-11-94-100. EDN: DNSBVC.

2. Shifrina Z.B., Rusanov A.L. Aromatic polyimides with flexible and rigid-rod chains. Uspekhi khimii = Russian Chemical Reviews. 1996;65(7):648-658. (In Russian). EDN: MOWEZR.

3. Lin B., Sundararaj U. Visualization of poly(ether imide) and polycarbonate blending in an internal mixer. Journal of Applied Polymer Science. 2004;92(2):1165-1175. https://doi.org/10.1002/app.20127.

4. Johnson R.O., Burlhis H.S. Polyetherimide: a new high-performance thermoplastic resin. Journal of Polymer Science: Polymer Symposia. 2007;70(1):129143. https://doi.org/10.1002/polc.5070700111.

5. Polyakov I.V., Vaganov G.V., Yudin V.E., Smirnova N.V., Ivan’kova E.M., Popova E.N. Study of polyetherimide and its nanocomposite 3D printed samples for biomedical application. Polymer Science. Series A. 2020;62(4):337-342. https://doi.org/10.1134/s0965545x20040094.

6. Cicala G., Ognibene G., Portues S., Blanc I., Rapisarda M., Pergolizzi E., et al. Comparison of Ultem 9085 used in fused deposition modelling (FDM) with polytherimide blends. Materials. 2018;11(2):285. https://doi.org/10.3390/ma11020285.

7. Padovano E., Galfione M., Concialdi P., Lucco G., Badini C. Mechanical and thermal behavior of Ultem® 9085 fabricated by fused-deposition modeling. Applied Sciences. 2020;10(9):3170. https://doi.org/10.3390/app10093170.

8. Zaldivar R.J., Witkin D.B., McLouth T., Patel D.N., Schmitt K., Nokes J.P. Influence of processing and orientation print effects on the mechanical and thermal behavior of 3D-printed Ultem® 9085 material. Additive Manufacturing. 2017;13:1-32. https://doi.org/10.1016/j.addma.2016.11.007.

9. White D.M., Takekoshi T., Williams F.J., Relles H.F., Donahue P.E., Klopfer H.J., et al. Polyetherimides via nitro-displacement polymerization: monomer synthesis and 13C-NMR analysis of monomers and polymers. Journal of Polymer Science: Polymer Chemistry Edition. 1981;19(7):1635-1658. https://doi.org/10.1002/pol.1981.170190705.

10. Takekoshi T. Synthesis of high performance aromatic polymers via nucleophilic nitro displacement reaction. Polymer Journal. 1987;19(1):191-202. https://doi.org/10.1295/polymj.19.191.

11. Korshak V.V., Rusanov A.L., Kazakova G.V., Zabelnikov N.S., Matvelashvili G.S. Nucleophilic nitro substitution reaction in the synthesis of polyimides. Vysokomolekulyarnye soedineniya = Polymer Science. 1988;30(9):1795-1814. (In Russian).

12. Rusanov A.L., Takekoshi T. Reactions using nitrocontaining monomers for the synthesis of aromatic polymers. Uspekhi khimii = Russian Chemical Reviews. 1991;60(7):738-750. (In Russian). https://doi.org/10.1070/RC1991v060n07ABEH001106.

13. Johnson D.S., Williams F.J., Scotia N.Y. Preparation of bisphenols-A bisimides. Patent USA, no. 4048190; 1977.

14. Johnson D.S., Scotia N.Y. Method for making aromatic bis(ether dicarboxylic acid)s. Patent USA, no. 4054600; 1977.

15. Zhubanov B.A., Arkhipova I.A., Shalabaeva I.D., Nikitina A.I., Matveev V.A., Fedotov Yu.A. Soluble thermoplastic polyetherimides. Vysokomolekulyarnye soedineniya = Polymer Science. 1993;35(2):152-156. (In Russian).

16. Antonov A.V., Kuznetsov A.A., Berendyaev V.I., Lavrov S.V., Gitina R.M., Kotov B.V. Thermal degradation of polyetherimides as influenced by the synthetic and testing conditions. Vysokomolekulyarnye soedineniya = Polymer Science. 1994;36(1):20-25. (In Russian).

17. Takekoshi T., Kochanowski J.E., Manello J.S., Webber M.J. Polyetherimides. II. High-temperature solution polymerization. Journal of Polymer Science: Polymer Symposia. 1986;74(1):93-108. https://doi.org/10.1002/polc.5070740111.

18. Krizhanovskaya A.I., Antonova M.M., Yakovleva V.A., Kostikova N.A., Morozova O.T. Method for producing a-methyl-4-nitrophthalimide using 65% nitric acid. Khimiya i tekhnologiya organicheskikh veshchestv. 2022;21(1):4-11. (In Russian). EDN: DOVTWS.

19. Vasilevskaya T.N., Yakovleva O.D., Kobrin V.S. A convenient method of N-methylphthalimide synthesis. Synthetic Communications. 1995;25(16):2463-2465. https://doi.org/10.1080/00397919508015451.

20. Williams F.J., Scotia N.Y. Process for separating N-methyl-4-nitrophthalimides. Patent USA, no. 3923828; 1974.

21. Takekosi T., Kochanovskij D.E. Method for producing polyetherimides. Patent RF, no. 674677; 1979. (In Russian).

22. Gofman I.V., Meleshko T.K., Bogorad N.N., Sklizkova V.P., Kudryavtsev V.V. Long-term stability of physical and mechanical properties of heat-resistant polyimides films. Vysokomolekulyarnye soedineniya = Polymer Science. 2004;46(7):1776-1884. (In Russian).

23. Adrova N.A., Artyukhov A.I., Baklagina Yu.G., Borisova T.I., Koton M.M., Kuvshinskii E.V., et al. Structure and relaxation properties of polyetheramidoxylates during their imidization. Vysokomolekulyarnye soedineniya = Polymer Science. 1972;14(10):21662173. (In Russian).