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Curing kinetics, thermal and adhesive properties of phthalonitrile/aromatic diamine systems

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Abstract

The present work reports on the synthesis of an easily processable phthalonitrile monomer (BBPN) with isobutyl segment. The effect of various curing agents on curing behaviors, thermal and adhesive properties of BBPN has been evaluated. The novel phthalonitrile monomer was synthesized through nucleophilic substitution of 2,2-bis(4-hydroxyphenyl)butane (BPB) and 4-nitrophthalonitrile, and its chemical structure was characterized with FTIR, 1H NMR and 13C NMR analyses. Four different aromatic diamines derived from different catalytic activities such as p-phenylenediamine (p-PD), m-tolidine (m-TB), o-tolidine (o-TB), and 2,2′-bis(trifluoromethyl)benzidine (TFMB) were used as curing agents. The curing kinetics of BBPN/aromatic diamine samples were investigated by non-isothermal differential scanning calorimetry (DSC) at different heating rates. The average activation energy was calculated based on Kissinger’s and Ozawa’s methods varied in the range of 66.61–79.00 kJ mol−1. The thermal properties of the obtained polymers were investigated by dynamic mechanical thermal analysis (DMA) and thermogravimetric analysis (TGA). Compared to other three systems, the cured BBPN/p-PD exhibited better thermal stability and higher glass-transition temperature (Tg), suggesting its higher degree of cross-linking. Moreover, the BBPN/diamine systems were used to bond aluminum sheet, and the average values of lap shear strengths were in the range of 13.8–19.6 MPa at room temperature and 9.2–11.5 MPa at 300 °C, respectively.

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References

  1. Sastri SB, Keller TM (1998) Phthalonitrile cure reaction with aromatic diamines. J Polym Sci Part A Polym Chem 36:1885–1890

    CAS  Google Scholar 

  2. Zhang B, Luo Z, Zhou H, Liu F, Yu R, Pan Y, Wang Y, Zhao T (2012) Addition-curable phthalonitrile-functionalized novolac resin. High Perform Polym 24:398–404

    Google Scholar 

  3. Laskoski M, Dominguez DD, Keller TM (2013) Alkyne-containing phthalonitrile resins: controlling mechanical properties by selective curing. J Polym Sci Part A Polym Chem 51:4774–4778

    CAS  Google Scholar 

  4. Wang AR, Dayo AQ, Zu LW, Lv D, Song S, Tang T, Liu WB, Wang J, Gao BC (2018) Bio-based phthalonitrile compounds: synthesis, curing behavior, thermomechanical and thermal properties. React Funct Polym 127:1–9

    CAS  Google Scholar 

  5. Jia K, Xu M, Zhao R, Liu X (2011) Chemically bonded iron carbonyl for magnetic composites based on phthalonitrile polymers. Polym Int 60:414–421

    CAS  Google Scholar 

  6. Jiang M, Xu M, Jia K, Liu X (2016) Copolymerization of self-catalyzed phthalonitrile with bismaleimide toward high-temperature-resistant polymers with improved processability. High Perform Polym 28:895–907

    CAS  Google Scholar 

  7. Xu M, Liu M, Dong S, Liu X (2013) Design of low temperature self-cured phthalonitrile-based polymers for advanced glass fiber composite laminates. J Mater Sci 48:8108–8116

    CAS  Google Scholar 

  8. Tong L, Pu Z, Chen Z, Huang X, Liu X (2014) Effect of nanosilica on the thermal, mechanical, and dielectric properties of polyarylene ether nitriles terminated with phthalonitrile. Polym Compos 35:344–350

    CAS  Google Scholar 

  9. Augustine D, Mathew D, Reghunadhan Nair CP (2015) End-functionalized thermoplastic-toughened phthalonitrile composites: influence on cure reaction and mechanical and thermal properties. Polym Int 64:146–153

    CAS  Google Scholar 

  10. Zong L, Liu C, Zhang S, Wang J, Jian X (2015) Enhanced thermal properties of phthalonitrile networks by cooperating phenyl-s-triazine moieties in backbones. Polymer 77:177–188

    CAS  Google Scholar 

  11. Sheng H, Peng X, Guo H, Yu X, Naito K, Qu X, Zhang Q (2014) Synthesis of high performance bisphthalonitrile resins cured with self-catalyzed 4-aminophenoxy phthalonitrile. Thermochim Acta 577:17–24

    CAS  Google Scholar 

  12. Tong L, Jia K, Liu X (2015) A novel single-component composite based on phthalonitrile end-capped polyarylene ether nitrile: crystallization and crosslinking. J Polym Res 22:125

    Google Scholar 

  13. Laskoski M, Keller TM, Qadri SB (2007) Direct conversion of highly aromatic phthalonitrile thermosetting resins into carbon nanotube containing solids. Polymer 48:7484–7489

    CAS  Google Scholar 

  14. Bulgakov BA, Sulimov AV, Babkin AV, Kepman AV, Malakho AP, Avdeev VV (2017) Dual-curing thermosetting monomer containing both propargyl ether and phthalonitrile groups. J Appl Polym Sci 133:44786

    Google Scholar 

  15. Xu M, Ren D, Chen L, Li K, Liu X (2018) Understanding of the polymerization mechanism of the phthalonitrile-based resins containing benzoxazine and their thermal stability. Polymer 143:28–39

    CAS  Google Scholar 

  16. Sheng L, Yin C, Xiao J (2016) A novel phthalonitrile monomer with low post cure temperature and short cure time. RSC Adv 6:22204–22212

    CAS  Google Scholar 

  17. Badshah A, Kessler MR, Heng Z, Zaidi JH, Hameed S, Hasan A (2013) An efficient approach to prepare ether and amide-based self-catalyzed phthalonitrile resins. Polym Chem UK 4:3617–3622

    CAS  Google Scholar 

  18. Selvakumar P, Sarojadevi M (2009) Development of oligomeric phthalonitrile resins for advanced composite applications. Macromol Symp 277:190–200

    CAS  Google Scholar 

  19. Han Y, Tang D, Wang G, Guo Y, Zhou H, Qiu W, Zhao T (2019) Low melting phthalonitrile resins containing methoxyl and/or allyl moieties: synthesis, curing behavior, thermal and mechanical properties. Eur Polym J 111:104–113

    CAS  Google Scholar 

  20. Bulgakov BA, Babkin AV, Dzhevakov PB, Bogolyubov AA, Sulimov AV, Kepman AV, Kolyagin YG, Guseva DV, Rudyak VY, Chertovich AV (2016) Low-melting phthalonitrile thermosetting monomers with siloxane-and phosphate bridges. Eur Polym J 84:205–217

    CAS  Google Scholar 

  21. Babkin AV, Zodbinov EB, Bulgakov BA, Kepman AV, Avdeev VV (2016) Thermally stable phthalonitrile matrixes containing siloxane fragments. Polym Sci Ser B 58:298–306

    CAS  Google Scholar 

  22. Zhao F, Liu R, Yu X, Naito K, Qu X, Zhang Q (2015) A high temperature polymer of phthalonitrile-substituted phosphazene with low melting point and good thermal stability. J Appl Polym Sci 132:42606

    Google Scholar 

  23. Zhao F, Liu R, Kang C, Yu X, Naito K, Qu X, Zhang Q (2014) A novel high-temperature naphthyl-based phthalonitrile polymer: synthesis and properties. RSC Adv 4:8383–8390

    CAS  Google Scholar 

  24. Zou X, Xu M, Jia K, Liu X (2014) Synthesis, polymerization, and properties of the allyl-functional phthalonitrile. J Appl Polym Sci 131:41203

    Google Scholar 

  25. Laskoski M, Neal A, Schear MB, Keller TM, Ricks-Laskoski HL, Saab AP (2015) Oligomeric aliphatic-aromatic ether containing phthalonitrile resins. J Polym Sci Part A Polym Chem 53:2186–2191

    CAS  Google Scholar 

  26. Laskoski M, Dominguez DD, Keller TM (2005) Synthesis and properties of a bisphenol A based phthalonitrile resin. J Polym Sci Part A Polym Chem 43:4136–4143

    CAS  Google Scholar 

  27. Dominguez DD, Keller TM (2006) Low-melting phthalonitrile oligomers: preparation, polymerization and polymer properties. High Perform Polym 18:283–304

    CAS  Google Scholar 

  28. Liu C, Sun M, Zhang B, Zhang X, Li J, Wang L, Xue G, Zhao M, Song C, Li Q (2017) Preparation and properties of acetylene-terminated benzoxazine/epoxy copolymers. React Funct Polym 120:98–103

    CAS  Google Scholar 

  29. Liu C, Sun M, Zhang B, Zhang X, Li J, Li Q (2017) Curing kinetics, thermal, and adhesive properties of acetylene-terminated benzoxazine. J Appl Polym Sci 134:44547

    Google Scholar 

  30. Chen C, Wang J, Chen X, Yu X, Zhang Q (2019) Improvement of thermal conductivities and mechanical properties for polyphthalonitrile nanocomposites via incorporating functionalized h-BN fillers. High Perform Polym 31:294–303

    CAS  Google Scholar 

  31. Keller TM, Dominguez DD (2005) High temperature resorcinol-based phthalonitrile polymer. Polymer 46:4614–4618

    CAS  Google Scholar 

  32. Yang X, Zhang J, Lei Y, Zhong J, Liu X (2011) Effect of different aromatic amines on the crosslinking behavior and thermal properties of phthalonitrile oligomer containing biphenyl ethernitrile. J Appl Polym Sci 121:2331–2337

    CAS  Google Scholar 

  33. Keller TM (1988) Phthalonitrile-based high temperature resin. J Polym Sci Part A Polym Chem 26:3199–3212

    CAS  Google Scholar 

  34. Chen YP, Dayo AQ, Zhang HY, Wang AR, Wang J, Liu WB, Yan Y, Qin QR, Yang YG (2019) Synthesis of cardanol-based phthalonitrile monomer and its copolymerization with phenol-aniline-based benzoxazine. J Appl Polym Sci 136:47505

    Google Scholar 

  35. Xu J, Wang H, Zhang Z, Yang K, Li P, Chen X, Yu X, Naito K, Zhang Q (2019) Synthesis and properties of a high-performance pyrimidine-containing self-catalyzed phthalonitrile polymer. J Polym Sci Part A Polym Chem 57:2287–2294

    CAS  Google Scholar 

  36. Liu Y, Ji P, Zhang Z, Yu X, Naito K, Zhang Q (2019) Synthesis and properties of pyrazine-based oligomeric phthalonitrile resins. High Perform Polym 31:1075–1084

    CAS  Google Scholar 

  37. Sen P, Yıldız SZ, Atalay VE, Kanmazalp SD, Dege N (2019) Synthesis, molecular structure, spectroscopic and computational studies on 4-(2-(2-(2-formylphenoxy)ethoxy)ethoxy)phthalonitrile as functionalized phthalonitrile. Maced J Chem Chem Eng 38:63–74

    Google Scholar 

  38. Sastri SB, Keller TM (1999) Phthalonitrile polymers: cure behavior and properties. J Polym Sci Part A Polym Chem 37:2105–2111

    CAS  Google Scholar 

  39. Keller TM, Price TR (1982) Amine-cured bisphenol-linked phthalonitrile resins. J Macromol Sci Chem 18:931–937

    Google Scholar 

  40. Ando S, Matsuura T, Sasaki S (1992) 15N-, 1H-, and 13C-NMR chemical shifts and electronic properties of aromatic diamines and dianhydrides. J Polym Sci Part A Polym Chem 30:2285–2293

    CAS  Google Scholar 

  41. Zhou H, Badashah A, Luo Z, Liu F, Zhao T (2011) Preparation and property comparison of ortho, meta, and para autocatalytic phthalonitrile compounds with amino group. Polym Adv Technol 22:1459–1465

    Google Scholar 

  42. Ji S, Yuan P, Hu J, Sun R, Zeng K, Yang G (2016) A novel curing agent for phthalonitrile monomers: curing behaviors and properties of the polymer network. Polymer 84:365–370

    CAS  Google Scholar 

  43. Liu M, Jia K, Liu X (2015) Effective thermal conductivity and thermal properties of phthalonitrile-terminated poly(arylene ether nitriles) composites with hybrid functionalized alumina. J Appl Polym Sci 132:41595

    Google Scholar 

  44. Robert TM, Augustine D, Mathew D, Nair CR (2015) Graphene oxide induced fast curing of amino novolac phthalonitrile. RSC Adv 5:1198–1204

    CAS  Google Scholar 

  45. Rao BS, Palanisamy A (2013) Synthesis of bio based low temperature curable liquid epoxy, benzoxazine monomer system from cardanol: thermal and viscoelastic properties. Eur Polym J 49:2365–2376

    CAS  Google Scholar 

  46. Ishida H, Allen DJ (1996) Mechanical characterization of copolymers based on benzoxazine and epoxy. Polymer 37:4487–4495

    CAS  Google Scholar 

  47. Lin CH, Wang CS (2001) Novel phosphorus-containing epoxy resins. Part I. Synthesis and properties. Polymer 42:1869–1878

    CAS  Google Scholar 

  48. Liu W, Qiu Q, Wang J, Huo Z, Sun H, Zhao X (2009) Preparation and properties of one epoxy system bearing fluorene moieties. J Appl Polym Sci 113:1289–1297

    CAS  Google Scholar 

  49. Chen ZK, Yang G, Yang JP, Fu SY, Ye L, Huang YG (2009) Simultaneously increasing cryogenic strength, ductility and impact resistance of epoxy resins modified by n-butyl glycidyl ether. Polymer 50:1316–1323

    CAS  Google Scholar 

  50. Kolanadiyil SN, Bijwe J, Varma IK (2013) Synthesis of itaconimide/nadimide-functionalized benzoxazine monomers: structural and thermal characterization. React Funct Polym 73:1544–1552

    Google Scholar 

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Acknowledgements

We gratefully acknowledge the financial support from the Excellent Youth Foundation of Heilongjiang Province, PR China (Grant No. 51073049).

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Correspondence to Bin Zhang.

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Liu, C., Sun, M., Zhang, B. et al. Curing kinetics, thermal and adhesive properties of phthalonitrile/aromatic diamine systems. Iran Polym J 29, 67–75 (2020). https://doi.org/10.1007/s13726-019-00775-7

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