Synthesis of a boron modified phenolic resin

Kawamoto, Aparecida M.; Pardini, Luiz Cláudio; Diniz, Milton Faria; Lourenço, Vera Lúcia; Takahashi, Marta Ferreira K.

doi:10.5028/jatm.2010.02027610

Abstract:

Phenolic resin has long been used as matrix for composites mainly because of its flame retardant behavior and high char yield after pyrolysis, which results in a self supporting structure. The addition of ceramic powders, such as SiC and B₄C, as fillers to the phenolic resin, results in better thermo-oxidative stability, but as drawbacks, it has poor homogeneity, adhesion and processing difficulties during molding of the composites. The addition of single elements, such as boron, silicon and phosphorus in the main backbone of the thermo-set resin is a new strategy to obtain special high performance resins, which results in higher mechanical properties, avoiding the drawbacks of simply adding fillers, which results in enhanced thermo-oxidative stability compared to conventional phenol-formaldehyde resins. Therefore, the product can have several applications, including the use as ablative thermal protection for thermo-structural composites. This work describes the preparation of a boron-modified phenolic resin (BPR) using salicyl alcohol and boric acid. The reaction was performed in refluxing toluene for a period of four hours, which produced a very high viscosity amber resin in 90% yield.The final structure of the compound, the boric acid double, substituted at the hydroxyl group of the aromatic ring, was determined with the help of the Infrared Spectroscopy, ¹H-NMR, TGA-DSC and boron elemental analysis. The absorption band of the group B-O at 1349 cm^-1 can be visualized at the FT-IR spectrum. ¹H-NMR spectra showed peaks at 4.97-5.04 ppm and 3.60-3.90 ppm assigned to belong to CH₂OH groups from the alcohol. The elemental analysis was also performed for boron determination.The product has also been tested in carbon and silicon fibers composite for the use in thermal structure. The results of the tests showed composites with superior mechanical properties when compared with the conventional phenolic resin.

Keywords:
Phenolic resin; Boron; Thermal protection; Oxidizing agents

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REFERENCES

Abdalla, M.O., Ludwick, A., Mitchell, T., 2003, "Boron-modified phenolic resin for high performance applications", Polymer, Vol. 44, pp. 7353-7359.
America Patash Chem Corp., 1964, "British patent 957611"..
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Clayton, W.A., Fabish, T.J., Lagedrost, J.F., 1969, "Thermal Conductivity of Phenolic Chars. Technical Report AFML-TR-69-313", Air Force Materials Laboratory, Wright Air Force Base, Ohio-USA.
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» https://doi.org/10.1016/S0141-3910(96)00171-1
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Publication Dates

Publication in this collection
May-Aug 2010

History

Received
14 June 2010
Accepted
28 June 2010

This is an Open Access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

[1] Abdalla, M.O., Ludwick, A., Mitchell, T., 2003, "Boron-modified phenolic resin for high performance applications", Polymer, Vol. 44, pp. 7353-7359.

[2] America Patash Chem Corp., 1964, "British patent 957611"..

[3] Ancelotti Jr., A.C., 2006, "Efeitos da porosidade na resistência ao cisalhamento e nas propriedades dinâmicas de compósitos de fibra de carbono/resina epóxi", Master of Science dissertation, Intituto Tecnológico de Aeronáutica, São José dos Campos, SP, Brazil.

[4] Bonner, J.G., Hope, P.S., 1993, "Compatibilities and reactive blending". In: Folkes, M.J., Hope, P.S., "Polymer blends and alloys", Blackie Academic and Professional, London, pp.46-74.

[5] Casiraghi, G., et al., 1980, "Selective Reactions between Phenols and Formaldehyde. A Superior Synthesis of Salicyl Alcohols", Synthesis, Vol. 2, pp. 124-125.

[6] Castro, L.D., 1991, "Inhibition of Oxidation of Carbon Materials". PhD Thesis, University of Bath, UK.

[7] Clayton, W.A., Fabish, T.J., Lagedrost, J.F., 1969, "Thermal Conductivity of Phenolic Chars. Technical Report AFML-TR-69-313", Air Force Materials Laboratory, Wright Air Force Base, Ohio-USA.

[8] Costa, L., et al., 1997, "Structure-charring relationship in phenol-formaldehyde type resins". Polymer Degradation and Stability, Vol. 56, No 1, pp. 23-35. doi: 10.1016/S0141-3910(96)00171-1.
» https://doi.org/10.1016/S0141-3910(96)00171-1

[9] Fahrenholtz, S.R., Kwei, T.K., 1981, "Compatibility of polymer mixtures containing novolac resins", Macromolecules, Vol. 14, pp. 1076-1079.

[10] Gao, J.G., Liu, Y.F., Yang, L.T., 1999, "Thermal stability of boron-containing phenolformaldehyde resin" Polymer Degradation and Stability, Vol. 63, pp. 19-22.

[11] Gao, J.G., Liu, Y.F., Yang, F.L., 2001, "Structure and properties of boron-containing bisphenol-A formaldehyde resin", European Polymer Journal, Vol. 37, pp. 207-210.

[12] Grenier-Loustalot, M.F., et al., 1996, "Phenolic resins .2. Influence of catalyst type on reaction mechanisms and kinetics", Polymer, Vol. 37, No 8, pp. 1363-1369.

[13] Hirohata, T., Misaki, T., Yoshii, T.M., 1987, "Improvement of flame retardance and heat resistance of bromine, chlorine and boron modified phenolic resins", J Soc Mater Sci Jpn (Engl Transl), Vol. 36, No 401, pp. 184-188.

[14] Knop, A., Sheib, W., 1979, "Chemistry and application of phenolic resins", Springer-Verlag, Berlin.

[15] Knop, A., Pilato, L.A., 1985, "Phenolic resins", Springer-Verlag, Berlin.

[16] Lemon, P.H.R.B., 1985, "Phenol formaldehyde polymers for the bonding of refractories", Brit. Ceram. Trans. J., Vol. 84, Nº. 2, pp. 53-56.

[17] Lenghaus, K., Qiao, G.G., Solomon, D.H., 2000, "Model studies of the curing of resole phenol-formaldehyde resins.Part I.The behaviour of ortho quinone methide in a curing resin", Polymer, Vol. 41, No.6, pp. 1973-1979.

[18] McKee, D.W., 1991, "Oxidation protection of carbon materials", In: Thrower, P.A., editor, "Chemistry and physics of carbon", Vol. 23, pp. 173-232.

[19] Liu, C.L., et al., 2007, "Evolution of microstructure and properties of phenolic fibers during carbonization", Materials Science and Engineering A, Vol. 459, No 1-2, pp. 347-354.

[20] Okoroafor, E.U., Villemaire, J.P., Agassant, J.F.,1992, "The viscosity of immiscible polymer blends:influences of the interphase and deformability", Polymer, Vol. 33, No 24, pp. 5264-5271.

[21] Park, B.D., et al., "Polymer", 1999, Vol. 40, N 7, pp. 1689-1699

[22] Santos, W.N., Mummery, P., Wallwork, A., 2005, "Thermal diffusivity of polymers by the laser flash technique", Polymer testing, Vol. 24, No 5, pp. 628-634.

[23] Schmidt, D.L., Graig, R.D., 1982, "Advanced Carbon Fabric-Phenolic for Thermal Protection Application", AFWAL US, AFWAL-TR-81-4136, USA.

[24] Segal, C.L., 1967, "High Temperature Polymers", Marcel Dekker, New York.

[25] Serio, M.A., et al., 1991, "Pyrolysis of phenol-formaldehyde resin: experiments and modeling". ACS Div. Fuel Chem. Prepr., Vol. 36, No 2, p. 664.

[26] Smith, A.L, 1999, "Infrared Spectroscopy", John Wiley & Sons, Hoboken, NJ, USA.

[27] US Army Armament Research, Development, and Engineering Center, SMCAR-BAC-S, 1991, "Military Handbook 754 (AR) Plastic Matrix Composites with Continuous Fiber Reinforcement", Picatinny Arsenal, Dover, NJ, USA.

[28] United States Patent and Trademark Office 4 045 398, 1977.

[29] Whitehouse, A.A.K., Pritchett, E.G.K., Barnett, G., 1968, "Phenolic Resins", Iliffe Books Ltd., London; American Elsevier, New York.

Brasil