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Preparation and properties of halogen-free flame retardant epoxy resins with phosphorus-containing siloxanes

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Abstract

Novel epoxy resin modifiers, DOPO–TMDS and DOPO–DMDP were synthesized by addition reaction of divinylsiloxane with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO). Halogen-free flame retardant epoxy resins were obtained through modification of o-cresol novolac epoxy resin cured by phenol novolac resin using DOPO–TMDS and DOPO–DMDP which were characterized by 1H NMR, 13C NMR, 31P NMR and FT-IR measurements. Effects of the phosphorus-containing siloxanes on thermal stabilities, mechanical properties and flame retardant properties of the epoxy resins were investigated. The cured epoxy resins exhibited better mechanical properties and greatly improved flame retardant properties due to the presence of phosphorus-containing siloxanes. The cured epoxy resins with phosphorus loading of 2.0 wt% showed LOI values of 32–33 and achieved UL94V-0 ratings.

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References

  1. Lee H, Neville K (eds) (1972) Handbook of epoxy resins. McGraw-Hill, New York

    Google Scholar 

  2. McAdams LV, Gannon JA (1988) Encyclopedia of Polymer Science and Engineering, vol 6. Wiley, New York, p 322

    Google Scholar 

  3. Bergman A (1999) In: Proceedings of international conference on halogen-free materials for electronic and electric products, Gotherburg, Sweden

  4. Hsiue GH, Liu YL, Tsiao J (2000) Phosphorus-containing epoxy resins for flame retardancy V: synergistic effect of phosphorus–silicon on flame retardancy. J Appl Polym Sci 78:1

    Article  CAS  Google Scholar 

  5. Li J, Chen S, Xu X (1990) Mechanism of flame-retardant action of tris (2,3-dichloropropyl) phosphate on epoxy resin. J Appl Polym Sci 40:417

    Article  CAS  Google Scholar 

  6. Liu YI, Pearce EM, Weil ED (1999) Flame retardancy of dicyandiamide-crosslinked epoxy resins containing phenolphthalein structures and/or a phosphorus-containing additive. J Fire Sci 17:240

    Article  CAS  Google Scholar 

  7. Zerda AS, Lesser AJ (2002) Organophosphorous additive for fortification, processibility, and flame retardance of epoxy resins. J Appl Polym Sci 84:302

    Article  CAS  Google Scholar 

  8. Kodolov VI, Shuklin SG, Kuznetsov AP, Makarova LG, Bystrov SG, Demicheva OV, Rudakova TA (2002) Formation and investigation of epoxy intumescent compositions modified by active additives. J Appl Polym Sci 85:1477

    Article  CAS  Google Scholar 

  9. Denq BL, Hu YS, Chen LW, Chiu WY, Wu TR (1999) The curing reaction and physical properties of DGEBA/DETA epoxy resin blended with propyl ester phosphazene. J Appl Polym Sci 74:229

    Article  CAS  Google Scholar 

  10. Lin CH, Feng CC, Hwang TY (2007) Preparation, thermal properties, morphology, and microstructure of phosphorus containing epoxy/SiO2 and polyimide/SiO2 nanocomposites. Eur Polym J 43:725

    Article  CAS  Google Scholar 

  11. Wang XD, Zhang Q (2004) Synthesis, characterization, and cure properties of phosphorus-containing epoxy resins for flame retardance. Eur Polym J 40:385

    Article  CAS  Google Scholar 

  12. Lin CH, Wu CY, Wang CS (2000) Synthesis and properties of phosphorus-containing advanced epoxy resins. II. J Appl Polym Sci 78:228

    Article  CAS  Google Scholar 

  13. Wang CS, Shieh JY (1998) Synthesis and properties of epoxy resins containing 2-(6-oxid-6H-dibenz<c,e> <1,2>oxaphosphorin-6-yl)1,4-benzenediol. Polymer 39:5819

    Article  CAS  Google Scholar 

  14. Cho CS, Fu SC, Chen LW, Wu TR (1998) Aryl phosphinate anhydride curing for flame retardant epoxy networks. Polym Int 47:203

    Article  CAS  Google Scholar 

  15. Liu YL, Wu CS, Hsu KY, Chang TC (2002) Flame-retardant epoxy resins from o-cresol novolac epoxy cured with a phosphorus containing aralkyl novolac. J Polym Sci Polym Chem 40:2329

    Article  CAS  Google Scholar 

  16. Wang CS, Lin CH (1998) Properties and curing kinetic of diglycidyl ether of bisphenol A cured with a phosphorus-containing diamine. J Appl Polym Sci 74:1635

    Article  Google Scholar 

  17. Levchik SV, Weil ED (2004) Thermal decomposition, combustion and flame-retardancy of epoxy resins—a review of the recent literature. Polym Int 53:1901

    Article  CAS  Google Scholar 

  18. Hsiue GH, Wang WJ, Chang FC (1999) Synthesis, characterization, thermal and flame-retardant properties of silicon-based epoxy resins. J Appl Polym Sci 73:1231

    Article  CAS  Google Scholar 

  19. Kashiwagi T, Gilman JW (2000) In: Grand AF, Wilkie GA (eds) Fire retardancy of polymeric materials. Marcel Dekker, New York

    Google Scholar 

  20. Hsiue GH, Wei HF, Shiao SJ, Kuo WJ, Sha YA (2001) Chemical modification of dicyclopentadiene-based epoxy resins to improve compatibility and thermal properties. Polym Degrad Stab 73:309

    Article  CAS  Google Scholar 

  21. Mercado LA, Reina JA, Galia M (2006) Flame retardant epoxy resins based on diglycidyloxymethylphenylsilane. J Polym Sci Polym Chem 44:5580

    Article  CAS  Google Scholar 

  22. Li Q, Jiang PK, Su ZP, Wei P, Wang GL, Tang XZ (2005) Synergistic effect of phosphorus, nitrogen, and silicon on flame-retardant properties and char yield in polypropylene. J Appl Polym Sci 96:854

    Article  CAS  Google Scholar 

  23. Anna P, Marosi G, Bourbigot S, Le Bras M, Delobel R (2002) Intumescent flame retardant systems of modified rheology. Polym Degrad Stab 77:243

    Article  CAS  Google Scholar 

  24. Han LB, Zhao CQ (2005) Stereospecific addition of H–P bond to alkenes: a simple method for the preparation of (Rp)-phenylphosphinates. J Org Chem 70:10121

    Article  CAS  Google Scholar 

  25. Tang LX, Qu BJ, Shen XF (2004) Mechanical properties, morphological structure, and thermal behavior of dynamically photocrosslinked PP/EPDM blends. J Appl Polym Sci 92:3371

    Article  CAS  Google Scholar 

  26. Wu CS, Liu YL, Chiu YC, Chiu YS (2002) Thermal stability of epoxy resins containing flame retardant components: an evaluation with thermogravimetric analysis. Polym Degrad Stab 78:41

    Article  CAS  Google Scholar 

  27. Troitsch J (1990) International plastic flammability handbook, 2nd edn. Hanser, Munich

    Google Scholar 

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Acknowledgment

The authors wish to thank for financial support of National Natural Science Foundation of China (Project Grant No. 50803069).

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Correspondence to Zhiqiang Tao or Shiyong Yang.

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Ding, J., Tao, Z., Zuo, X. et al. Preparation and properties of halogen-free flame retardant epoxy resins with phosphorus-containing siloxanes. Polym. Bull. 62, 829–841 (2009). https://doi.org/10.1007/s00289-009-0052-0

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