Abstract
Hydroxy-containing low molecular weight poly(2,6-dimethyl-1,4-phenylene oxide) (rPPO) and self-promoted hydroxycontaining phthalonitrile (HPPH) were prepared by redistribution reaction and the simple nucleophilic displacement of a nitro-substituent from 4-nitrophthalonitrile in a dipolar aprotic solvent respectively. The hydroxy-containing phthalonitriles modified by rPPO were prepared by mechanical blending without compatibilizer, followed by heating. The curing behavior was studied using dynamic rheological analysis, and the results showed that the rPPO-modified phthalonitrile exhibited a large processing window (over −67 °C) and complex viscosity (0.18−0.8 Pa·s) at moderate temperatures. After curing at 300 °C, the resulting polymers showed good thermal stability and high modulus as observed by thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA). The dielectric properties and the morphology of rPPO-modified phthalonitrile networks were studied by dielectric analysis and field-emission scanning electron microscopy (SEM).
Article PDF
Similar content being viewed by others
Explore related subjects
Discover the latest articles, news and stories from top researchers in related subjects.Avoid common mistakes on your manuscript.
References
Seike, Y.; Okude, Y.; Iwakura, I.; Chiba, I.; Ikeno. T.; Yamada, T. Synthesis of polyphenylene ether derivatives: estimation of their dielectric constants. Macromol. Chem. Phys. 2003, 204(15), 1876–1881.
Liang, G. Z.; Meng, J.; Zhao, L. Synthesis of styrene-maleic anhydride random copolymer and its compatibilization to poly(2,6-dimethyl-1,4-phenylene ether)/brominated epoxy resin. Polym. Int. 2010, 52(6), 966–972.
Hwang, H. J.; Hsu, S. W.; Wang, C. S. Synthesis and physical properties of low-molecular-weight redistributed poly(2,6-dimethyl-1,4-phenylene oxide) for epoxy resin. J. Appl. Polym. Sci. 2008, 110(3), 1880–1890.
Su, C. T.; Lin, K. Y.; Lee, T. J.; Liang, M. Preparation, characterization and curing properties of epoxy-terminated poly(alkyl-phenylene oxide)s. Eur. Polym. J. 2010, 46(7), 1488–1497.
Ishii, Y.; Ryan, A. J. Processing of poly(2,6-dimethyl-1, 4-phenylene ether) with epoxy resin. 1. Reaction-induced phase separation. Macromolecules 2000, 33(1), 158–166.
Zeng, K.; Zhou, K.; Zhou, S. H.; Hong, H. B.; Zhou, H. F.; Wang, Y. P.; Miao, P. K.; Yang, G. Studies on self-promoted cure behaviors of hydroxy-containing phthalonitrile model compounds. Eur. Polym. J. 2009, 45(4), 1328–1335.
Laskoski, M.; Dominguez, D. D.; Keller, T. M. Synthesis and properties of a bisphenol A based phthalonitrile resin. J. Polym. Sci., Part A: Polym. Chem. 2005, 43(18), 4136–4143.
Dominguez, D. D.; Keller, T. M. Phthalonitrile-epoxy blends: cure behavior and copolymer properties. J. Appl. Polym. Sci. 2010, 110(4), 2504–2515.
Sastri, S. B.; Keller, T. M. Phthalonitrile polymers: cure behavior and properties. J. Polym. Sci., Part A: Polym. Chem. 1999, 37(13), 2105–2111.
Augustine, D.; Mathew, D.; Nair, C. P. R. Phenol-containing phthalonitrile polymers-synthesis, cure characteristics and laminate properties. Polym. Int. 2013, 62(7), 1068–1076.
Lv, J. B.; Ma, J. Z.; Cheng, K.; Chen, C.; Hu, J. H.; Zeng, K.; Yang, G. New insights into phthalonitrile/epoxy blends modification system from non-competitive cure system based on alicyclic anhydride. Chinese J. Polym. Sci. 2017, DOI: 10.1007/s10118-017-1992-8
Zhou, H.; Badashah, A.; Luo, Z. H., Liu, F.; Zhao, T. Preparation and property comparison of ortho, meta, and para autocatalytic phthalonitrile compounds with amino group. Polym. Advan. Technol. 2011, 22(10), 1459–1465
Laskoski, M.; Dominguez, D. D. Keller, T. M. Synthesis and properties of aromatic ether phosphine oxide containing oligomeric phthalonitrile resins with improved oxidative stability. Polymer 2007, 48(21), 6234–6240.
Sastri, S. B.; Armistead, J. P.; Keller, T. M. Phthalonitrilecarbon fiber composites. Polym. Compos. 1996, 17(6), 816–822
Sastri, S. B.; Armistead, J. P.; Keller, T. M. Phthalonitrile-glass fabric composites. Polym. Compos. 1997, 18(1), 48–54.
Dominguez, D. D.; Jones, H. N.; Keller, T. M. The effect of curing additive on the mechanical properties of phthalonitrile-carbon fiber composites. Polym. Compos. 2004, 25(5), 554–561.
Keller, T. M.; Price, T. R. Amine-cured bisphenol-linked phthalonitrile resins. J. Macromol. Sci. Chem. 1982, 18(6), 931–937.
Burchill, P. J. On the formation and properties of a high-temperature resin from a bisphthalonitrile. J. Polym. Sci., Part A: Polym. Chem. 1994, 32(1), 1–8.
Keller, T. M.; Griffith, J. R. The synthesis of a new class of polyphthalocyanine resins. J. Am. Chem. Soc. 1980, 132, 25–34.
Walton, T. R.; Griffith, J. R.; O’Rear, J. G. Adhesion science and technology. J. Adhes. Sci. Technol. 1975, 9, 665–676.
Yuan, P.; Ji, S. C.; Hu, J. H.; Hu, X. P.; Zeng, K.; Yang, G. Systematic study on highly efficient thermal synergistic polymerization effect between alicyclic imide moiety and phthalonitrile: scope, properties and mechanism. Polymer 2016, 102, 266–280.
Ji, S. C.; Yuan, P.; Hu, J. H.; Sun, R.; Zeng, K.; Yang, G. A novel curing agent for phthalonitrile monomers: Curing behaviors and properties of the polymer network. Polymer 2016, 84, 365–370.
Hu, J. H.; Wu, D. M.; Lu, D. K.; Xiang, S. R.; Zhao, Y. C.; Zeng, K.; Yang, G. Study on thermal behaviors of a novel cruciform amide-containing phthalonitrile monomer. Des. Monomers Polym. 2015, 18(7), 620–626.
Hu, J. H.; Liu, Y. C.; Jiao, Y.; Ji, S. C.; Sun, R.; Yuan, P.; Zeng, K.; Pu, X. M.; Yang, G. Self-promoted phthalimidecontaining phthalonitrile resins with sluggish curing process and excellent thermal stability. RSC Adv. 2015, 5(21), 16199–16206.
Wu, D. M.; Zhao, Y. C.; Zeng, K.; Yang, G. A novel benzimidazole-containing phthalonitrile monomer with unique polymerization behavior. J. Polymr. Sci., Part A: Polym. Chem. 2012, 50(23), 4977–4982.
Sastri, S. B.; Keller, T. M. Phthalonitrile cure reaction with aromatic diamines. J. Polym. Sci., Part A: Polym. Chem. 1998, 36(11), 1885–1890.
Zeng, K.; Zhou, K.; Tang, W. R.; Tang, Y.; Zhou, H. F.; Liu, T.; Wang, Y. P.; Zhou, H. B.; Yang, G. Synthesis and curing of a novel amino-containing phthalonitrile derivative. Chinese Chem. Lett. 2007, 18(5), 523–526.
Laskoski, M.; Keller, T. M.; Ricks-Laskoski, H. L.; Giller, C. B.; Hervey, J. Improved synthesis of oligomeric sulfone-based phthalonitriles. Macromol. Chem. Phys. 2015, 216(17), 1808–1815.
Kaliavaradhan, K.; Muthusamy, S. Synthesis and characterization of various phenylene diamine-based bismaleimide-containing phthalonitrile resins. Polym. Bull. 2016, 7(73), 1921–1938.
Wang, J. B.; Hu, J. H.; Zeng, K.; Yang, G. Preparation of self-promoted hydroxy-containing phthalonitrile resins by an in situ reaction. RSC Adv. 2015, 5(127), 105038–105046.
Bolon, D. A. Free-radical redistribution of phenol dimers. J. Org. Chem. 1967, 32(5), 1584–1590.
Aert, H. A. M. V.; Genderen, M. H. P. V.; Steenpaal, G. J. M. L. V.; Nelissen, L.; Meijer, E. W. Modified poly(2,6-dimethyl-1,4-phenylene ether)s prepared by redistribution. Macromolecules 1997, 30(20), 6056–6066.
Baesjou, P. J.; Driessen, W. L.; Challa, G.; Reedijk, J. A kinetic and spectroscopic study on the copper catalyzed oxidative coupling polymerization of 2,6-dimethylphenol. X-ray structure of the catalyst precursor tetrakis (N-methylimidazole) bis(nitrato) copper(II). J. Mol. Catal. A-Chem. 1996, 110(3), 195–210.
Hay, A. S. Polymerization by oxidative coupling: discovery and commercialization of PPO and noryl resins. J. Polym. Sci., Part A: Polym. Chem. 1998, 36(4), 505–517.
Viersen, F. J.; Challa, G.; Reedijk, J. Mechanistic studies of the oxidative coupling polymerization of 2,6-dimethylphenol: 4. Mechanism of polymer formation catalysed by a copper(II)-tmed complex. Polymer 1990, 31(7). 1368–1373.
Scoponi, M.; Pradella, F.; Kaczmarek, H.; Amadelli, R.; Carassiti, V. A reappraisal of the photo-oxidation mechanism at short and long wavelengths for poly(2,6-dimethyl-1,4-phenylene oxide). Polymer 1996, 37(6), 903–916.
Li, X. G. High-resolution thermogravimetry of poly(2, 6-dimethyl-1,4-phenylene oxide). J. App. Polym. Sci. 1999, 71(11), 1887–1892.
Blanco, I.; Cicala, G.; Latteri, A.; Mamo, A.; Recca, A. Thermal and thermo-oxidative degradations of poly (2,6-dimethyl-1,4-phenylene oxide) (PPO)/copoly(aryl ether sulfone) P(ESES-co-EES) block copolymers: a kinetic study. J. Therm. Anal. Calorim. 2013, 112(1), 375–381.
Saron, C.; Sanchez, E.; Isabel Felisberti, M. Thermal and photochemical degradation of PPO/HIPS blends. J. Appl. Polym. Sci. 2007, 104(5), 3269–3276.
Saron, C.; Felisberti, M. I. Dynamic mechanical spectroscopy applied to study the thermal and photodegradation of poly(2,6-dimethyl-1,4-phenylene oxide)/high impact polystyrene blends. Mat. Sci. Eng. A 2004, 370(1), 293–301.
Acknowledgments
This work was financially supported by the National Natural Science Foundation of China (Nos. 51203098 and 51173114).
Author information
Authors and Affiliations
Corresponding authors
Rights and permissions
About this article
Cite this article
Ma, JZ., Cheng, K., Lv, JB. et al. Phthalonitrile-PPO Blends: Cure Behavior and Properties. Chin J Polym Sci 36, 497–504 (2018). https://doi.org/10.1007/s10118-018-2026-x
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10118-018-2026-x