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Phthalonitrile-PPO Blends: Cure Behavior and Properties

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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).

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References

  1. 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.

    Article  CAS  Google Scholar 

  2. 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.

    Article  Google Scholar 

  3. 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.

    Article  CAS  Google Scholar 

  4. 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.

    Article  CAS  Google Scholar 

  5. 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.

    Article  CAS  Google Scholar 

  6. 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.

    Article  CAS  Google Scholar 

  7. 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.

    Article  CAS  Google Scholar 

  8. Dominguez, D. D.; Keller, T. M. Phthalonitrile-epoxy blends: cure behavior and copolymer properties. J. Appl. Polym. Sci. 2010, 110(4), 2504–2515.

    Article  Google Scholar 

  9. Sastri, S. B.; Keller, T. M. Phthalonitrile polymers: cure behavior and properties. J. Polym. Sci., Part A: Polym. Chem. 1999, 37(13), 2105–2111.

    Article  CAS  Google Scholar 

  10. 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.

    CAS  Google Scholar 

  11. 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

    Google Scholar 

  12. 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

    Article  Google Scholar 

  13. 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.

    Article  CAS  Google Scholar 

  14. Sastri, S. B.; Armistead, J. P.; Keller, T. M. Phthalonitrilecarbon fiber composites. Polym. Compos. 1996, 17(6), 816–822

    Article  CAS  Google Scholar 

  15. Sastri, S. B.; Armistead, J. P.; Keller, T. M. Phthalonitrile-glass fabric composites. Polym. Compos. 1997, 18(1), 48–54.

    Article  CAS  Google Scholar 

  16. 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.

    Article  CAS  Google Scholar 

  17. Keller, T. M.; Price, T. R. Amine-cured bisphenol-linked phthalonitrile resins. J. Macromol. Sci. Chem. 1982, 18(6), 931–937.

    Article  Google Scholar 

  18. 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.

    Article  CAS  Google Scholar 

  19. Keller, T. M.; Griffith, J. R. The synthesis of a new class of polyphthalocyanine resins. J. Am. Chem. Soc. 1980, 132, 25–34.

    CAS  Google Scholar 

  20. Walton, T. R.; Griffith, J. R.; O’Rear, J. G. Adhesion science and technology. J. Adhes. Sci. Technol. 1975, 9, 665–676.

    Article  Google Scholar 

  21. 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.

    Article  CAS  Google Scholar 

  22. 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.

    Article  CAS  Google Scholar 

  23. 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.

    Article  CAS  Google Scholar 

  24. 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.

    Article  CAS  Google Scholar 

  25. 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.

    Article  CAS  Google Scholar 

  26. Sastri, S. B.; Keller, T. M. Phthalonitrile cure reaction with aromatic diamines. J. Polym. Sci., Part A: Polym. Chem. 1998, 36(11), 1885–1890.

    Article  CAS  Google Scholar 

  27. 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.

    Article  CAS  Google Scholar 

  28. 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.

    Article  CAS  Google Scholar 

  29. Kaliavaradhan, K.; Muthusamy, S. Synthesis and characterization of various phenylene diamine-based bismaleimide-containing phthalonitrile resins. Polym. Bull. 2016, 7(73), 1921–1938.

    Article  Google Scholar 

  30. 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.

    Article  CAS  Google Scholar 

  31. Bolon, D. A. Free-radical redistribution of phenol dimers. J. Org. Chem. 1967, 32(5), 1584–1590.

    Article  CAS  Google Scholar 

  32. 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.

    Article  Google Scholar 

  33. 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.

    Article  CAS  Google Scholar 

  34. 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.

    Article  CAS  Google Scholar 

  35. 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.

    Article  CAS  Google Scholar 

  36. 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.

    Article  CAS  Google Scholar 

  37. Li, X. G. High-resolution thermogravimetry of poly(2, 6-dimethyl-1,4-phenylene oxide). J. App. Polym. Sci. 1999, 71(11), 1887–1892.

    Article  CAS  Google Scholar 

  38. 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.

    Article  CAS  Google Scholar 

  39. Saron, C.; Sanchez, E.; Isabel Felisberti, M. Thermal and photochemical degradation of PPO/HIPS blends. J. Appl. Polym. Sci. 2007, 104(5), 3269–3276.

    Article  CAS  Google Scholar 

  40. 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.

    Article  Google Scholar 

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Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (Nos. 51203098 and 51173114).

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Authors and Affiliations

  1. State Key Laboratory of Polymer Materials Engineering, College of Polymer Science and Engineering, Sichuan University, Chengdu, 610065, China

    Jing-Zhi Ma, Kang Cheng, Jiang-Bo Lv, Chang Chen, Jiang-Huai Hu, Ke Zeng & Gang Yang

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  1. Jing-Zhi Ma
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  2. Kang Cheng
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  3. Jiang-Bo Lv
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  4. Chang Chen
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  6. Ke Zeng
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Correspondence to Ke Zeng or Gang Yang.

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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

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  • DOI: https://doi.org/10.1007/s10118-018-2026-x

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