A novel fluorinated phthalonitrile monomer is synthesized via nucleophilic substitution reactions using 4,4′-difluorobenzophenone, bisphenol AF, and 4-nitrophthalimide. Two resins with distinct curing temperatures are obtained using 4-(aminophenoxy) benzonitrile (APPH) as the curing agent. The successful synthesis of the monomer is confirmed by nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy (FTIR). Differential scanning calorimetry (DSC) is employed to determine the melting point and curing behavior of the monomer, revealing a melting point of 102°C and a calculated processing window of 148°C. Furthermore, a relatively low average apparent activation energy was calculated. The morphology of the polymer cross-section was characterized using scanning electron microscopy (SEM), and the resin cross-section exhibited characteristics consistent with brittle fracture. Thermodynamic properties of the polymers are investigated via dynamic mechanical analysis (DMA), revealing storage modulus of 2313 MPa and 2433 MPa for the two resins at room temperature. Thermal stability is evaluated by thermogravimetric analysis (TGA), revealing that both resins exhibited temperatures for 5% weight loss above 500°C under both nitrogen and air atmospheres.
RenDXuMChenS, et al.Curing reaction and properties of a kind of fluorinated phthalonitrile containing benzoxazine. Eur Polym J2021; 159: 110715. https://doi.org/10.1016/j.eurpolymj.2021.110715
2.
LiBXuXRenD, et al.Modification on phthalonitrile containing benzoxazine with hydroxy-terminated polyarylene ether nitrile: curing reaction and thermomechanical properties. Compos Commun2023; 43: 101734. https://doi.org/10.1016/j.coco.2023.101734
KumarDChoudharyV. Curing kinetics and thermal properties of imide containing phthalonitrile resin using aromatic amines. Thermochim Acta2020; 693: 178749. https://doi.org/10.1016/j.tca.2020.178749
6.
YuanPJiSHuJ, et al.Systematic study on highly efficient thermal synergistic polymerization effect between alicyclic imide moiety and phthalonitrile: Scope, properties and mechanism. Polymer2016; 102: 266–280. https://doi.org/10.1016/j.polymer.2016.09.025
7.
TongLPuZHuangX, et al.Crosslinking behavior of polyarylene ether nitrile terminated with phthalonitrile (PEN‐t‐Ph)/1,3,5‐Tri‐(3,4‐dicyanophenoxy) benzene (TPh) system and its enhanced thermal stability. J Appl Polym Sci2013; 130(2): 1363–1368. https://doi.org/10.1002/app.39312
8.
ZongLLiuCZhangS, et al.Enhanced thermal properties of phthalonitrile networks by cooperating phenyl-s-triazine moieties in backbones. Polymer2015; 77: 177–188. https://doi.org/10.1016/j.polymer.2015.09.035
9.
PengAWangZZengZ, et al.Self-catalytic bio-based benzoxazine-phthalonitrile thermosets with high heat resistance and flame retardancy. Polym Degrad Stabil2025; 241: 111612. https://doi.org/10.1016/j.polymdegradstab.2025.111612
10.
RuzickaEGRichardsonTJFordHO, et al.Next-generation electrically conductive phthalonitrile resins: design, synthesis, and processing. J Polym Sci2025; 64(1): 93–105. https://doi.org/10.1002/pol.20250461
11.
ChenXShanSLiuJ, et al.Synthesis and properties of high temperature phthalonitrile polymers based on o, m, p-dihydroxybenzene isomers. RSC Adv2015; 5(98): 80749–80755. https://doi.org/10.1039/c5ra15321b
12.
ChenZYangXXuM, et al.Preparation and properties of bisphenol A-based bisphthalonitrile polymers. High Perform Polym2013; 26(1): 3–11. https://doi.org/10.1177/0954008313493645
13.
JiaZZhangXWangX, et al.Structural design and synthesis of naphthalene-containing phthalonitrile polymer with excellent processability and high temperature properties. J Polym Sci2023; 61(19): 2292–2302. https://doi.org/10.1002/pol.20230295
14.
DominguezDDKellerTM. Low-melting phthalonitrile oligomers: preparation, polymerization and polymer properties. High Perform Polym2006; 18(3): 283–304. https://doi.org/10.1177/0954008306060143
15.
WangGHanYGuoY, et al.Phthalonitrile-terminated silicon-containing oligomers: synthesis, polymerization, and properties. Ind Eng Chem Res2019; 58(23): 9921–9930. https://doi.org/10.1021/acs.iecr.9b01642
HuJPuYZhouR, et al.Self-curing phthalonitrile resin with disulfide bond as the curing group. ACS Appl Polym Mater2023; 5(11): 9027–9036. https://doi.org/10.1021/acsapm.3c01485
18.
LiuCLiSYuanZ, et al.Low-melting maleimide-containing phthalonitrile resins: synthesis, curing behavior, and thermal performance. Polymer2024; 315: 127821. https://doi.org/10.1016/j.polymer.2024.127821
19.
MaARongJLiD, et al.Thermal stability and curing mechanism of self-catalytic bio-based phthalonitrile resins. Polymer2025; 336: 128916. https://doi.org/10.1016/j.polymer.2025.128916
20.
SunHLvYZhangC, et al.Materials with low dielectric constant and loss and good thermal properties prepared by introducing perfluorononenyl pendant groups onto poly(ether ether ketone). RSC Adv2018; 8(14): 7753–7760. https://doi.org/10.1039/c7ra13600e
21.
XiongXYaoLRenR, et al.Preparation and properties of high-temperature resistant bisphthalonitrile resins containing trifluoromethyl groups reinforced by poly (aryl ether nitrile) capped by phthalonitrile and their composites. High Perform Polym2024; 36(3): 143–152. https://doi.org/10.1177/09540083241229209
22.
DongJSangXYinW, et al.Preparation of fluorinated epoxy-phthalonitrile resins with excellent thermal stability and low dielectric constant. J Appl Polym Sci2023; 140(12): e53641. https://doi.org/10.1002/app.53641
23.
ChenSRenDLiB, et al.Benzoxazine containing fluorinated aromatic ether nitrile linkage: preparation, curing kinetics and dielectric properties. Polymers2019; 11(6): 1036. https://doi.org/10.3390/polym11061036
24.
ShengHPengXGuoH, et al.Synthesis of high performance bisphthalonitrile resins cured with self-catalyzed 4-aminophenoxy phthalonitrile. Thermochim Acta2014; 577: 17–24. https://doi.org/10.1016/j.tca.2013.12.010
25.
LvJHongJLiangB, et al.Study of the curing kinetics of melamine/phthalonitrile resin system. Thermochim Acta2020; 683: 178442. https://doi.org/10.1016/j.tca.2019.178442
LuKWeiWDWangJT. Grain growth kinetics and interfacial energies in nanocrystalline Ni-P alloys. J Appl Phys1991; 69(10): 7345–7347. https://doi.org/10.1063/1.347591
28.
WangHRGaoYLYeYF, et al.Crystallization kinetics of an amorphous zr–cu–ni alloy: calculation of the activation energy. J Alloys Compd2003; 353(1): 200–206. https://doi.org/10.1016/S0925-8388(02)01208-2
29.
StarinkMJ. A new method for the derivation of activation energies from experiments performed at constant heating rate. Thermochim Acta1996; 288(1): 97–104. https://doi.org/10.1016/S0040-6031(96)03053-5
30.
StarinkMJ. The determination of activation energy from linear heating rate experiments: a comparison of the accuracy of isoconversion methods. Thermochim Acta2003; 404(1): 163–176. https://doi.org/10.1016/S0040-6031(03)00144-8
31.
KolesnikovTIOrlovaAMTsegelskayaAY, et al.Dual-curing propargyl-phthalonitrile imide-based thermoset: synthesis, characterization and curing behavior. Eur Polym J2021; 161: 110865. https://doi.org/10.1016/j.eurpolymj.2021.110865
32.
ZhaoFLiuRKangC, et al.A novel high-temperature naphthyl-based phthalonitrile polymer: synthesis and properties. RSC Adv2014; 4(16): 8383–8390. https://doi.org/10.1039/C3RA46638H
33.
JiaDZhaoHRongJ, et al.High-performance quinoxaline-containing phthalonitrile resin: synthesis, curing kinetics, and properties. High Perform Polym2024; 36(5): 292–302. https://doi.org/10.1177/09540083241244466
34.
WangGHanYGuoY, et al.Phthalonitrile terminated fluorene based copolymer with outstanding thermal and mechanical properties. Eur Polym J2019; 113: 1–11. https://doi.org/10.1016/j.eurpolymj.2019.01.040
35.
YuXYNaitoKKangC, et al.Synthesis and properties of a high-temperature naphthyl-based phthalonitrile polymer. Macromol Chem Phys2013; 214(3): 361–369. https://doi.org/10.1002/macp.201200492
BaiSSunXZhangZ, et al.Synthesis and properties of A low melting point phthalonitrile resin containing high density nitrile groups. ChemistrySelect2020; 5(1): 265–269. https://doi.org/10.1002/slct.201903930
38.
OheHMatsuuraK. The relation between the heat of combustion and the oxygen index for high-polymeric materials. Textil Res J1975; 45(11): 778–784. https://doi.org/10.1177/004051757504501104
39.
LaskoskiMDominguezDDKellerTM. Synthesis and properties of a bisphenol a based phthalonitrile resin. J Polym Sci, Part A: Polym Chem2005; 43(18): 4136–4143. https://doi.org/10.1002/pola.20901
40.
HuRZhangFLuoL, et al.An end-capping strategy for shape memory phthalonitrile resins via annealing enables conductivity and wave-absorption. Chem Eng J2024; 489: 150956. https://doi.org/10.1016/j.cej.2024.150956
Supplementary Material
Please find the following supplemental material available below.
For Open Access articles published under a Creative Commons License, all supplemental material carries the same license as the article it is associated with.
For non-Open Access articles published, all supplemental material carries a non-exclusive license, and permission requests for re-use of supplemental material or any part of supplemental material shall be sent directly to the copyright owner as specified in the copyright notice associated with the article.
