Development of the technique for quality control of 1,3-bis(3,4-dicyanophenoxy)benzene by HPLC

Objectives. Determination of target products and byproducts is necessary for the quality control of phthalonitrile monomer synthesis as well as production scaling and performing related kinetic studies. High-performance liquid chromatography (HPLC) is a simple and affordable method for quantitative chemical analysis, which also verifies the quality of raw materials. The objective of this study was to develop an HPLC technique for determining the composition of the reaction mixture in the synthesis of 1,3-bis(3,4-dicyanophenoxy)benzene (DPB).

Methods. Reversed-phase HPLC was used to quantitatively analyze the reaction mixture.

Results. A simple and rapid method for the quantitative HPLC analysis of phthalonitrile monomers and their mixtures with reagents was developed. Reaction times and the accumulation of byproducts were also studied.

Conclusions. The successful performance of the developed technique allows us to recommend it for practical applications. The results obtained for reactors of different sizes have good convergence, and DPB synthesis was successfully scaled up to intermediate scale equipment.

1. Laskoski M., Neal A., Schear M.B., Keller T.M., RicksLaskovski H.L., Saab A.P. Oligomeric aliphatic-aromatic ether containing phthalonitrile resins. J. Polym. Sci. Part A Polym. Chem. 2015;53(18):2186–2191. https://doi.org/10.1002/pola.27659

2. Babkin A.V., Zodbinov E.B., Bulgakov B.A., Kepman A. V., Avdeev V.V. Low-melting siloxane-bridged phthalonitriles for heat-resistant matrices. Eur. Polym. J. 2015;66:452–457. https://doi.org/10.1016/j.eurpolymj.2015.03.015

3. Derradji M., Jun W., Wenbin L. Phthalonitrile resins and composites : properties and applications. 1st Edition. Elsevier; 2018. 404 p. ISBN: 9780128129661

4. Wang G., Guo Y., Han Y., Li Z., Ding J., Jiang H., Zhou H., Zhao T. Enhanced properties of phthalonitrile resins reinforced by novel phthalonitrile-terminated polyaryl ether nitrile containing fluorene group. High Perform. Polym. SAGE Publications Ltd. 2020;32(1):3–11. https://doi.org/10.1177/0954008319847259

5. Li Z., Guo Y., Wang G., Xu S., Yan Y., Liu X., Luo Z., Ye L., Zhou H., Zhao T. Preparation and characterization of a selfcatalyzed fluorinated novolac-phthalonitrile resin. Polym. Adv. Technol. 2018;29(12):2936–2942. https://doi.org/10.1002/pat.4413

6. Ren D., Lei Y., Pan H., Yan L., Xu M., Liu X. Design of the phthalonitrile-based composite laminates by improving the interfacial compatibility and their enhanced properties. J. Appl. Polym. Sci. 2018;135(7):45881. https://doi.org/10.1002/app.45881

7. Sastri S.B., Armistead J.P., Keller T.M. Phthalonitrilecarbon fiber composites. Polym. Compos. 1996;17(6):816–822. https://doi.org/10.1002/pc.10674

8. Bulgakov B.A., Babkin A.V., Dzhevakov P.B., Bogolyubov A.A., Sulimov A.V., Kepman A.V. Low-melting phthalonitrile thermosetting monomers with siloxane- and phosphate bridges. Eur. Polym. J. 2016;84:205–217. https://doi.org/10.1016/j.eurpolymj.2016.09.013

9. Yakovlev M.V., Morozov O.S., Afanasieva E.S., Bulgakov B.A., Babkin A.V., Kepman A.V. Tri-functional phthalonitrile monomer as stiffness increasing additive for easy processable high performance resins. React. Funct. Polym. 2020;146:104409. https://doi.org/10.1016/j.reactfunctpolym.2019.104409

10. Terekhov V.E., Aleshkevich V.V., Afanasieva E.S., Nechausov S. Bis(4-cyanophenyl) phenyl phosphate as viscosity reducing comonomer for phthalonitrile resins. React. Funct. Polym. 2019;139:34–41. https://doi.org/10.1016/j.reactfunctpolym.2019.03.010

11. Bulgakov B.A., Sulimov A.V., Babkin A.V., Timoshkin I.A., Solopchenko A.V., Kepman A.V. Phthalonitrile-carbon fiber composites produced by vacuum infusion process. J. Compos. Mater. 2017;51(30):4157–4164. https://doi.org/10.1177/0021998317699452

12. Timoshkin I.A.,Aleshkevich V.V.,Afanas’eva E.S., Bulgakov B.A., Babkin A.V., Kepman A.V. Heat-Resistant Carbon Fiber Reinforced Plastics Based on a Copolymer of Bisphthalonitriles and Bisbenzonitrile. Polym. Sci. Ser. C. 2020;62(2):172–182. http://doi.org/10.1134/S1811238220020150

13. Bulgakov B.A., Sulimov A.V., Babkin A.V., Afanasiev D.V., Solopchenko A.V., Kepman A.V. et al. Flame-retardant carbon fiber reinforced phthalonitrile composite for high-temperature applications obtained by resin transfer molding. Mendeleev Commun. 2017;27(3):257–259. https://doi.org/10.1016/j.mencom.2017.05.013

14. Bulgakov B.A., Belsky K.S., Nechausov S.S., Afanasieva E.S., Babkin A.V., Kepman A.V. Carbon fabric reinforced propargyl ether/phthalonitrile composites produced by vacuum infusion. Mendeleev Commun. 2018;28(1):44–46. https://doi.org/10.1016/j.mencom.2018.01.014

15. Keller T.M., Dominguez D.D. High temperature resorcinol-based phthalonitrile polymer. Polymer. 2005;46(13):4614–4618. https://doi.org/10.1016/j.polymer.2005.03.068

16. Lyubimtsev A., Vagin S., Syrbu S., Hanack M. Synthesis of Novel Covalently Linked Dimeric Phthalocyanines. European J. Org. Chem. 2007;2007(12):2000–2005. https://doi.org/10.1002/ejoc.200600733

17. Ryoichi F., Fumio O. Method for manufacturing 4,4’-oxydiphthalic acid and method for manufacturing 4,4’-oxydiphthalic dianhydride: pat. PCT/JP2012/057040. Japan. 26.09.2013.

18. Chen X., Shan S., Liu J., Quab X., Zhang Q. Synthesis and properties of high temperature phthalonitrile polymers based on o, m, p–dihydroxybenzene isomers. RSC Adv. 2015;5(98):80749–80755. https://doi.org/10.1039/C5RA15321B