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Synthesis and characterization of trifluoromethyl-containing polyimide-modified epoxy resins

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Abstract

Two series of epoxy resins modified with trifluoromethyl-containing poly(amic acid)s and polyimides, respectively, were prepared. The effects of trifluoromethyl group and imide unit on the properties of epoxy resins were investigated. The epoxy resins modified with poly(amic acid)s exhibited better performance because poly(amic acid)s serve as amine curing agent in epoxy resins and form chemical bond with epoxy matrix, thus having higher miscibility with epoxy resin than the epoxy resins modified with polyimides. The glass transition temperatures of the modified epoxy resins were in the range of 88.9–168.2 °C. Compared with unmodified epoxy resin, the modified epoxy resins exhibited better thermal stability with char yield at 800 °C ranging from 18 to 55 %, lower hydrophilicity with water absorption in the range of 0.47–0.95 %, and water contact angle of 94.9–105.0°. The introduction of trifluoromethyl group decreases the surface free energy and hydrophilicity of the modified epoxy resins. The SEM images of the fracture surfaces of the modified epoxy resins showed tough fracture features, indicating the enhancement of toughness of these resins in which imide unit had been introduced.

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References

  1. Goodman SH (1998) Handbook of thermoset plastics. Park Ridge, New Jersey

    Google Scholar 

  2. May CA, Tanaka Y (1988) Epoxy resins: chemistry and technology. Marcel Dekker, New York

    Google Scholar 

  3. Jin FL, Li X, Park SJ (2015) Synthesis and application of epoxy resins: a review. J Ind Eng Chem 29:1–11

    Article  Google Scholar 

  4. Jeon HR, Park JH, Shon MY (2013) Corrosion protection by epoxy coating containing multi-walled carbon nanotubes. J Ind Eng Chem 19:849–853

    Article  Google Scholar 

  5. Ozturk A, Kaynak C, Tincer T (2001) Effects of liquid rubber modification on the behaviour of epoxy resin. Eur Polym J 37:2353–2363

    Article  Google Scholar 

  6. Grubbs RB, Dean JM, Broz ME, Bates FS (2000) Reactive block copolymers for modification of thermosetting epoxy resins. Macromolecules 33:9522–9534

    Article  Google Scholar 

  7. Kaynak C, Sipahi-Saglama E, Akovali G (2001) A fractographic study on toughening of epoxy resin using ground tyre rubber. Polymer 42:4393–4399

    Article  Google Scholar 

  8. Chikhi N, Fellahi S, Bakar M (2002) Modification of epoxy resin using reactive liquid (ATBN) rubber. Eur Polym J 38:251–264

    Article  Google Scholar 

  9. Zeng M, Sun X, Xiao H, Ji G, Jiang X, Wang B, Qi C (2008) Investigation of free volume and the interfacial, and toughening behavior for epoxy resin/rubber composites by positron annihilation. Radiat Phys Chem 77:245–251

    Article  Google Scholar 

  10. Tang LC, Zhang H, Sprenger S, Ye L, Zhang Z (2012) Fracture mechanisms of epoxy-based ternary composites filled with rigid-soft particles. Compos Sci Technol 72:558–565

    Article  Google Scholar 

  11. Kinloch AJ, Mohammed RD, Taylor AC (2005) The effect of silica nano particles and rubber particles on the toughness of multiphase thermosetting epoxy polymers. J Mater Sci 40:5083–5086. doi:10.1007/s10853-0051716

    Article  Google Scholar 

  12. Yang L, Zhang C, Pilla S, Gong S (2008) Polybenzoxazine-core shell rubber–carbon nanotube nanocomposites. Composites Part A 39:1653–1659

    Article  Google Scholar 

  13. Liang YL, Pearson RA (2010) The toughening mechanism in hybrid epoxy–silica–rubber nanocomposites (HESRNs). Polymer 51:4880–4890

    Article  Google Scholar 

  14. Gómez-del Río T, Rodríguez J, Pearson RA (2014) Compressive properties of nanoparticle modified epoxy resin at different strain rates. Composites Part B 57:173–179

    Article  Google Scholar 

  15. Hodgkin JH, Simon GP, Varley RJ (1998) Thermoplastic toughening of epoxy resins: a critical review. Polym Adv Technol 9:3–10

    Article  Google Scholar 

  16. Pearson RA, Yee AF (1993) Toughening mechanisms in thermoplastic-modified epoxies: 1. Modification using poly(phenylene oxide). Polymer 34:3658–3670

    Article  Google Scholar 

  17. Mimura K, Ito H, Fujioka H (2000) Improvement of thermal and mechanical properties by control of morphologies in PES-modified epoxy resins. Polymer 41:4451–4459

    Article  Google Scholar 

  18. Jones AR, Watkins CA, White SR, Sottos NR (2015) Self-healing thermoplastic-toughened epoxy. Polymer 74:254–261

    Article  Google Scholar 

  19. Ghosh M (1996) Polyimides: fundamentals and applications. Marcel Dekker, New York

    Google Scholar 

  20. Liaw DJ, Wang KL, Huang YC, Lee KR, Lai JY, Ha CS (2012) Advanced polyimide materials: syntheses, physical properties and applications. Prog Polym Sci 37:907–974

    Article  Google Scholar 

  21. Li H, Liu J, Wang K, Fan L, Yang S (2006) Synthesis and characterization of novel fluorinated polyimides derived from 4, 4′-[2, 2, 2-trifluoro-1-(3, 5-ditrifluoromethylphenyl)ethylidene]diphthalic anhydride and aromatic diamines. Polymer 47:1443–1450

    Article  Google Scholar 

  22. Woo Y, Oh SY, Kang YS, Jung B (2003) Synthesis and characterization of sulfonated polyimide membranes for direct methanol fuel cell. J Membr Sci 220:31–45

    Article  Google Scholar 

  23. Fang J, Kita H, Okamoto KI (2000) Hyperbranched polyimides for gas separation applications. 1. Synthesis and characterization. Macromolecules 33:4639–4646

    Article  Google Scholar 

  24. Hay JN, Woodfine B, Davies M (1996) Toughening of epoxy resins by polyimides synthesized from bisanilines. High Perform Polym 8:35–56

    Article  Google Scholar 

  25. Ilijima T, Hamakawa S, Tomoi M (2001) Preparation of novel soluble poly(ester imide)s containing a trimellitimide moiety and their use as modifiers for aromatic diamine-cured epoxy resin. Polym Int 50:1214–1222

    Article  Google Scholar 

  26. Akhter T, Siddiqi HM, Akhter Z, Butt MS (2011) Synthesis and characterization of some polyimide-epoxy composites. E-Polymers 11:244–256

    Article  Google Scholar 

  27. Agag T, Takeichi T (1999) Synthesis and characterization of epoxy film cured with reactive polyimide. Polymer 40:6557–6563

    Article  Google Scholar 

  28. Biolley N, Pascal T, Sillion B (1994) Polyimide-modified epoxy resin: time-temperature-transformation diagrams, mechanical and thermal properties. Polymer 35:558–564

    Article  Google Scholar 

  29. Qiu Z, Wang J, Zhang Q, Zhang S, Ding M, Gao L (2006) Synthesis and properties of soluble polyimides based on isomeric ditrifluoromethyl substituted 1,4-bis(4-aminophenoxy)benzene. Polymer 47:8444–8452

    Article  Google Scholar 

  30. Thünemann AF, Lieske A, Paulke BP (1999) Low surface energy coatings from waterborne nano-dispersions of polymer complexes. Adv Mater 11:321–324

    Article  Google Scholar 

  31. Hougham G, Tesoro G, Shaw J (1994) Synthesis and properties of highly fluorinated polyimides. Macromolecules 27:3642–3649

    Article  Google Scholar 

  32. Lin SH, Li F, Cheng SZD, Harris FW (1998) Organo-soluble polyimides: synthesis and polymerization of 2,2′-bis(trifluoromethyl)-4,4′,5,5′-biphenyl tetracarboxylic dianhydride. Macromolecules 31:2080–2086

    Article  Google Scholar 

  33. Yang CP, Chen RS, Chen KH (2003) Light-colored and soluble fluorinated polyimides based on 2-trifluoromethyl-4,4′-diaminodiphenyl ether and various aromatic dianhydrides. Colloid Polym Sci 281:505–515

    Article  Google Scholar 

  34. Li H, Liu J, Wang K, Fan L, Yang S (2006) Synthesis and characterization of novel fluorinated polyimides derived from 4,4′-[2,2,2-trifluoro-1- (3,5-ditrifluoromethylphenyl)ethylidene]diphthalic anhydride and aromatic diamines. Polymer 47:1443–1450

    Article  Google Scholar 

  35. Urano Y, Chen N, Nakano K, Maeda K, Ando S (2008) Thermally stable multi-mode polymer optical waveguide fabricated by single-step photo-patterning of fluorinated polyimide/epoxy hybrids. In: Conference on organic photonic materials and devices X, 2008

  36. Chen F, Sun T, Song H, Meng K, Han CC (2008) Layered structure formation in the reaction-induced phase separation of epoxy/polyimide blends. Macromolecules 41:7469–7477

    Article  Google Scholar 

  37. Gopala A, Wu H, Heiden P (1998) Investigation of readily processable thermoplastic-toughened thermosets. III. Toughening BMIs and epoxy with a comb-shaped imide oligomer. J Appl Polym Sci 70:943–951

    Article  Google Scholar 

  38. Bakar M, Okulska-Bożek M, Zygmunt M (2011) Effect of poly(amic acid) and polyimide on the adhesive strength and fracture toughness of epoxy resin. Mater Sci 47:355–362

    Article  Google Scholar 

  39. Yeganeh H, Mehdipour-Ataei S, Ghaffari M (2008) Preparation and properties of novel poly(urethane-imide)s via blending of reactive polyimide and epoxy-terminated urethane prepolymers. High Perform Polym 20:126–145

    Article  Google Scholar 

  40. Ashcroft WR (1993) Chemistry and technology of epoxy resins. In: Ellis B (ed) Curing agents for epoxy resins. Springer, Glasgow, pp 37–71

    Google Scholar 

  41. Wang JY, Yang SY, Huang YL, Tien HW, Chin WK, Ma CCM, Shu WJ (2012) Synthesis and properties of trifluoromethyl groups containing epoxy resins cured with amine for low D k materials. J Appl Polym Sci 124:2615–2624

    Article  Google Scholar 

  42. Matsumoto A, Kimura T (1998) Synthesis of heat- and solvent-resistant polymers by radical polymerization of trifluoromethyl-substituted N-phenylmaleimides. J Appl Polym Sci 68:1703–1708

    Article  Google Scholar 

  43. Krishnan PSG, Vora RH, Chung TS (2001) Synthesis, characterization and kinetic study of hydrolysis of polyamic acid derived from ODPA and m-tolidine and related compounds. Polymer 42:5165–5174

    Article  Google Scholar 

  44. Chang JH, Park KM, Lee IC (2000) Thermal cyclodehydration of aromatic precursor polymers to polybenzoxazole and polyimide; their thermal and mechanical properties. Polym Bull 44:63–69

    Article  Google Scholar 

  45. Naito K, Onta M, Kogo Y (2012) The effect of adhesive thickness on tensile and shear strength of polyimide adhesive. Int J Adhes Adhes 36:77–85

    Article  Google Scholar 

  46. Glaris P, Coulon JF, Dorget M, Poncin-Epaillard F (2014) Fluorinated epoxy resin as a low adhesive mould for composite material. Composites Part B 63:94–100

    Article  Google Scholar 

  47. Miccio LA, Fasce DP, Schreiner WH, Montemartini PE, Oyanguren PA (2010) Influence of fluorinated acids bonding on surface properties of crosslinked epoxy-based polymers. Eur Polym J 46:744–753

    Article  Google Scholar 

Download references

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (51003033) and the Fundamental Research Funds for the Central Universities, SCUT (Grant Number 2015ZM100).

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  1. School of Materials Science and Technology, South China University of Technology, Guangzhou, 510641, China

    Xianfeng Que, Yurong Yan, Zhiming Qiu & Yang Wang

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  1. Xianfeng Que
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Correspondence to Zhiming Qiu.

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Que, X., Yan, Y., Qiu, Z. et al. Synthesis and characterization of trifluoromethyl-containing polyimide-modified epoxy resins. J Mater Sci 51, 10833–10848 (2016). https://doi.org/10.1007/s10853-016-0294-9

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