Deep eutectic solvent for curing of phthalonitrile resin: Lower the curing temperature but improve the properties of thermosetting

Abstract

Long curing duration and high curing temperature are commonly known to restrict the application of the phthalonitrile resin. In this study, a deep eutectic solvent (DES) containing ZnCl₂ and urea has been developed to improve the curing process of the resorcinol-based phthalonitrile resin (DPPh) without sacrificing the useful properties of the resin. For the molar ratio of ZnCl₂ and urea as 1:1 (ZnCl₂-urea (1–1)), the initial curing temperature and apparent activation energy of the system were recorded as 179.5°C and 90.1 kJ/mol, respectively, indicating a reduction of 31.2% and 39.0% as compared to the pristine ZnCl₂ system. More importantly, with curing time of 6 h and post-curing temperature of 300°C, the temperature at 5% weight loss as well as glass transition temperature of the resin with DES as the curing agent were 523.1°C and 370.2°C, respectively, demonstrating a significant improvement as compared to the resin cured with ZnCl₂. In addition, the satisfactory long-term oxidation stability of the resin could also be obtained by employing the new curing agent. The findings from this study open a functional pathway for facile preparation of the high-performance curing agent for the phthalonitrile resin.

Keywords

Phthalonitrile deep eutectic solvent low curing temperature high performance

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References

Keller

Dominguez

. High temperature resorcinol-based phthalonitrile polymer. Polymer 2005; 46: 4614–4618.

Sun

Lei

Guo

, et al. Enhanced mechanical properties at 400°C of carbon fabric reinforced phthalonitrile composites by high temperature postcure. Compos Part B: Eng 2019; 166: 681–687.

Bai

, et al. A high-performance functional phthalonitrile resin with a low melting point and a low dielectric constant. Soft Matter 2020; 16: 1888–1896.

Liu

Wang

, et al. Preparation and properties of poly(aryl ether ketone)-based phthalonitrile conductive composite film. High Perform Polym 2017; 31: 3–11.

Huang

Chen

, et al. Effect of nitrile-functionalization and thermal cross-linking on the dielectric and mechanical properties of PEN/CNTs–CN composites. J Mater Sci: Mater El 2013; 24: 2913–2922.

Yuan

, et al. A novel curing agent for phthalonitrile monomers: curing behaviors and properties of the polymer network. Polymer 2016; 84: 365–370.

Wang

Guo

Han

, et al. Enhanced properties of phthalonitrile resins reinforced by novel phthalonitrile-terminated polyaryl ether nitrile containing fluorene group. High Perform Polym 2019; 32: 3–11.

Laskoski

Neal

Keller

, et al. Improved synthesis of oligomeric phthalonitriles and studies designed for low temperature cure. J Polym Sci, Part A: Polym Chem 2014; 52: 1662–1668.

Zhao

Wang

, et al. Preparation and properties of phthalonitrile resins promoted by melamine. High Perform Polym 2017; 30: 561–570.

10.

Weng

Zong

, et al. Temperature for curing phthalonitrile-terminated poly(phthalazinone ether nitrile) reduced by a mixed curing agent and its curing behavior. RSC Adv 2015; 5: 92055–92060.

11.

Wang

Guo

, et al. A novel high temperature vinylpyridine-based phthalonitrile polymer with a low melting point and good mechanical properties. Polym Chem 2018; 9: 976–983.

12.

Cheng

, et al. The curing behavior and properties of phthalonitrile resins using ionic liquids as a new class of curing agents. Express Polym Lett 2017; 11: 924–934.

13.

Huang

Aromatic and heterocyclic dinitriles and their polymers. XI. Study on the polymerization of aromatic and heterocyclic dinitriles by infrared spectroscopy. Chin J Polym Sci 1985; 3(3): 226–234.

14.

Wang

Liu

, et al. Soluble and curable poly(phthalazinone ether amide)s with terminal cyano groups and their crosslinking to heat resistant resin. Polymer 2009; 50: 1700–1708.

15.

Han

, et al. Improving the curing process and thermal stability of phthalonitrile resin via novel mixed curing agents. Polym Int 2017; 66: 876–881.

16.

Weng

, et al. Enhanced properties of phthalonitrile resins under lower curing temperature via complex curing agent. Polym Advan Technol 2020; 31: 233–239.

17.

Zhang

De Oliveira Vigier

Royer

, et al. Deep eutectic solvents: syntheses, properties and applications. Chem Soc Rev 2012; 41: 7108–7146.

18.

Smith

Abbott

Ryder

. Deep eutectic solvents (DESs) and their applications. Chem Rev 2014; 114: 11060–11082.

19.

Abbott

Barron

Ryder

, et al. Eutectic-based ionic liquids with metal-containing anions and cations. Chem Eur J 2007; 13: 6495–6501.

20.

Rodriguez Rodriguez

Machiels

Binnemans

. p-Toluenesulfonic acid-based deep-eutectic solvents for solubilizing metal oxides. ACS Sustain Chem Eng 2019; 7: 3940–3948.

21.

Foreman

MRSJ

Holgersson

McPhee

, et al. Activity coefficients in deep eutectic solvents: implications for the solvent extraction of metals. New J Chem 2018; 42: 2006–2012.

22.

Sirviö

Hyypiö

Asaadi

, et al. High-strength cellulose nanofibers produced via swelling pretreatment based on a choline chloride–imidazole deep eutectic solvent. Green Chem 2020; 22: 1763–1775.

23.

Wang

Yao

Geng

, et al. Deep eutectic solvents as highly active catalysts for the fast and mild glycolysis of poly(ethylene terephthalate)(PET). Green Chem 2015; 17: 2473–2479.

24.

Dindarloo Inaloo

Majnooni

. Carbon dioxide utilization in the efficient synthesis of carbamates by deep eutectic solvents (DES) as green and attractive solvent/catalyst systems. New J Chem 2019; 43: 11275–11281.

25.

Carriazo

Serrano

Gutierrez

, et al. Deep-eutectic solvents playing multiple roles in the synthesis of polymers and related materials. Chem Soc Rev 2012; 41: 4996–5014.

26.

Ruiz-Olles

Slavik

Whitelaw

, et al. Self-assembled gels formed in deep eutectic solvents: supramolecular Eutectogels with high ionic conductivity. Angew Chem Int Edit 2019; 58: 4173–4178.

27.

Jaumaux

Liu

Zhou

, et al. Deep-eutectic-solvent-based self-healing polymer electrolyte for safe and long-life lithium-metal batteries. Angew Chem Int Edit 2020; 59: 9134–9142.

28.

Zhong

Tang

Zhu

, et al. An alternative electrolyte of deep eutectic solvent by choline chloride and ethylene glycol for wide temperature range supercapacitors. J Power Sources 2020; 452: 227847.

29.

Mąka

Spychaj

Kowalczyk

. Imidazolium and deep eutectic ionic liquids as epoxy resin crosslinkers and graphite nanoplatelets dispersants. J Appl Polym Sci 2014; 131: 40401.

30.

Mąka

Spychaj

Adamus

. Lewis acid type deep eutectic solvents as catalysts for epoxy resin crosslinking. RSC Adv 2015; 5: 82813–82821.

31.

Lionetto

Timo

Frigione

. Curing kinetics of epoxy-deep eutectic solvent mixtures. Thermochim Acta 2015; 612: 70–78.

32.

Tellers

Willems

Tjeerdsma

, et al. Eutectic hardener from food-based chemicals to obtain fully bio-based and durable thermosets. Green Chem 2020; 22: 3104–3110.

33.

Zheng

Dong

Wang

, et al. Electrodeposition of zinc coatings from the solutions of zinc oxide in imidazolium chloride/urea mixtures. Sci China Chem 2012; 55: 1587–1597.

34.

Jubsilp

Damrongsakkul

Takeichi

, et al. Curing kinetics of arylamine-based polyfunctional benzoxazine resins by dynamic differential scanning calorimetry. Thermochim Acta 2006; 447: 131–140.

35.

Zhang

Wang

Derradji

, et al. Synthesis, curing kinetics and thermal properties of a novel self-promoted fluorene-based bisphthalonitrile monomer. Thermochim Acta 2015; 602: 22–29.

36.

Vyazovkin

Burnham

Criado

, et al. ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data. Thermochim Acta 2011; 520: 1–19.

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