Synthesis and Application of a Novel Intumescent Flame Retardant Containing Ferrocenyl

Abstract:

A novel intumescent flame retardant (IFR) containing ferrocene and caged bicyclic phosphate groups, 1-oxo-4-[4'-(ferrocene carboxylic acid phenyl ester)] amide-2, 6, 7-trioxa-1-phosphabicyclo- [2.2.2] octane (PFAM), was successfully synthesized. The synthesized PFAM were added to flammable polyurethane (PU) as flame retardants and smoke suppressants. The structure of PFAM was characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (¹H NMR) and elemental analysis. Thermal stability of PFAM was tested by themogravimetric analysis (TGA). The results revealed that PFAM had good thermal stability and high char weight, the char weight up to 54% at 600 °C. Flammability properties of PU/PFAM composites were investigated by limiting oxygen index (LOI) test and UL-94 test, respectively. The results of LOI tests showed that the addition of PFAM enhanced flame retardancy of PU. When the content of PFAM reaches to 3%, the LOI value is 22.2. The morphologies of the char for PU and PU/3% PFAM composite can be obtained after LOI testing were examined by SEM. The results demonstrated that PFAM could promote to form the compact and dense intumescent char layer. Experiments showed that, the PFAM application of polyurethane showed positive effect.

• Periodical: Advanced Materials Research (Volumes 1033-1034)
• Pages: 931-936
• DOI: https://doi.org/10.4028/www.scientific.net/AMR.1033-1034.931
• Online since: October 2014
• Authors: Cong Yan Chen*, Rui Lan Fan, Guan Qun Yun
• Keywords: Ferrocene, Intumescent Flame Retardant, Polyurethane, Synthesis

References

[1] Chattopadhyay DK, Webster DC. Thermal stability and flame retardancy of polyurethanes. Prog. Polym 2007; 104: 3347.

[2] Horazcek H, Pieh S. The importance of intumescent systems for fire protection of plastic materials. Polym. Int 2000; 49: 1106.

DOI: 10.1002/1097-0126(200010)49:10<1106::aid-pi539>3.0.co;2-i

[3] Singh H, Jain AK. Ignition, combustion, toxicity, and fire retardancy of polyurethane foams : A comprehensive review. Appl. Polym 2009; 111: 1115.

DOI: 10.1002/app.29131

[4] Lv P, Wang ZZ, Hu KL, et al. Flammability and thermal degradation of flame retarded polypropylene composites containing melamine phosphate and pentaerythritol derivatives. Polym. Degrade. Stab 2005; 90(3): 523-524.

DOI: 10.1016/j.polymdegradstab.2005.04.003

[5] Qian Y, Wei P, Jiang P, et al. Synthesis of a novel hybrid synergistic flame retardant and its application in PP/IFR. Polym Degrad Stab 2011; 96: 1134-1140.

DOI: 10.1016/j.polymdegradstab.2011.02.017

[6] Song PG, Shen Y, Du BX, et al. Effects of reactive compatibilization on the morphological , thermal , mechanical , and rheological properties of intumescent flame-retardant polypropylene. Applied. Materials. & Interfaces 2009; 2(1): 452-459.

DOI: 10.1021/am8001204

[7] Wang RB, Ge ZX, Yao ZL. Synthesis and Characterization of Pentaerythritol phosphate flame retardant phosphorus oxychloride shrink melamine. Applied Chemical 2009; 38(10): 1434-1436.

[8] Zhang GH. Applied research in halogen-free intumescent flame retardant polypropylene. Modified plastics 2011; 8: 67-68.

[9] Xu JZ, Liu CH, Qu HQ, et. al. Investigation on the thermal degradation of flexible poly(vinyl chloride) filled with ferrites as flame retardant and smoke suppressant using TGA-FTIR and TGA-MS. Polym Degrad Stab 2013; 98: 1506-1514.

DOI: 10.1016/j.polymdegradstab.2013.04.016

[10] Li GX, Yang JF, He TS. An investigation of the thermal degradation of the intumescent coating containing MoO3 and Fe2O3. Surf Coating Technol 2008; 202: 3121.

DOI: 10.1016/j.surfcoat.2007.11.016

[11] Lv P, Wang ZZ, Hu Y. Effect of metallic oxides in polypropylene composites melamime phosphate and pentaerythritol. Plas Rubber Compos 2008; 37: 311.

DOI: 10.1179/174328908x314325

[12] Zhang P, Hu Y, Song L, et al. Synergistic effect of iron and intumescent flame retardant on shape-stabilized phase change material. Thermochimica Acta 2009; 487.

DOI: 10.1016/j.tca.2009.01.006

[13] Wang JS, Liu Y, Zhao HB, et al. Metal compound-enhanced flame retardancy of intumescent epoxy resins containing ammonium polyphosphate. Polym. Degrade. Stab 2009; 94(4): 625.

DOI: 10.1016/j.polymdegradstab.2009.01.006

[14] Lewin M, Endo M. Catalysis of intumescent flame retardancy of polypropylene by metallic compounds . Poly. Adv. Technol 2003; 14: 3.

DOI: 10.1002/pat.265

[15] Song RJ, Zhang BY, Huang BT, et al. Synergistic effect of supported nickel catalyst with intumescent flame-retardants on flame retardancy and thermal stability of polypropylene. J. Appl. Polym. Sci 2006; 102: 5988.

DOI: 10.1002/app.25178

[16] Mohajeri NN, Nelson G, Benrashid R. Synthesis and properties of new ferrocene-modified urethane block copolymers. J. Appl. Polym. Sci 2000; 76(13): 1847.

DOI: 10.1002/(sici)1097-4628(20000624)76:13<1847::aid-app1>3.0.co;2-m

[17] Carty P, Docherty A. Iron-containing Compouds as Flame Retarding/Smoke-suppressing Additives for PVC. FIRE AND MATERIALS 1988; 12: 109.

DOI: 10.1002/fam.810120305

[18] Carty P, Adger BM. Iron-containing organometallic compouds as flame-retarding smoke-suppressing additives for semi-rigid poly(vinyl chlorid). Applied Organometallic Chemistry 1990; 4: 127.

DOI: 10.1002/aoc.590040207

[19] Carty P, White S. A synergistic organoiron flame-retarding/smoke-suppressing system for ABS. Applied Organometallic Chemisty 1991; 5: 51.

DOI: 10.1002/aoc.590050107

[20] Carty P, Grant J, Metcalfet E, Povey DC. The preparation and structure of 1, 4, 5, 6, 7, 7-hexachloro-2-endo-ferrocenyhydroxyl-3-endo-hydroxymethyl-5-norbornene. Applied Organometallic Chemisty 1989; 3: 189.

DOI: 10.1002/aoc.590030212

[21] Carty P, Metcalfet EF, Annison WN. The optimization of the smoke suppressant and flame retardant properties of flexible PVC. Journal of Applied Polymer Science 1990; 41: 901.

DOI: 10.1002/app.1990.070410502

[22] Carty P, Grantt J, Metalfe E. Flame-retardancy and smoke-suppression studies on ferrocene derivatives in PVC. Applied Organometallic Chemisty 1996; 10: 101.

DOI: 10.1002/(sici)1099-0739(199603)10:2<101::aid-aoc484>3.0.co;2-7

[23] Carty P, Grant TG, Simpson A. Synthesis of a novel ferrocene derivative having flame-retardant and smoke-suppressant properties. Applied Organometallic Chemistry 1988; 2: 277.

DOI: 10.1002/aoc.590020311

[24] Ling BG, Bian ZX, Hu R, Zhao HY. Synthesis of ferrocene derivatives 2003; 52.

[25] Ma HY, Tong LF, Xu ZB, et al. A novel intumescent flame retardant: Synthesis and application in ABS copolymer. Polym Degrad Stab 2007; 92: 720-726.

DOI: 10.1016/j.polymdegradstab.2006.12.009