Abstract
Three phosphorous functional groups were introduced in one structural unit of polymer backbone to enhance the flame retardancy of PU coatings. In the first step, we synthesized tetramethylene bis(orthophosphate) (TBOP) that contained two phosphorus functional groups in one structural unit. In the next step, we synthesized modified polyesters (ATBTP-10,-20,-30) that contained triphosphorous groups by condensing polymerization of TBOP, 1,4-butanediol, trimethylolpropane, adipic acid, and phenylphosphonic acid (PPA). The amount of PPA in the ATBTPs was 10, 20, and 30 wt%. Then, flame-retardant PU coatings (AHFC−10,−20,−30) were prepared by curing ATBTPs with hexamethylene diisocyanate-biuret (curing agent) at room temperature. From the TGA analysis of diphosphorus-modified polyester (ATBT) and ATBTPs, the residues of ATBT, ATBTP-10, ATBTP-20, and ATBTP-30 were 24.6, 27.5, 29.2, and 31.9%, respectively. From this result, it was found that the residue increased in relation to the amount of PPA. Physical properties of the films of flame-retardant coatings were deteriorated with the addition of PPA (flame retarding component), however, all the films of flame-retardant coatings, except AHFC-30, met the required physical properties standard for coatings. Char lengths of the AHFCs measured by the 45° Meckel burner method were 2.9∼4.8 cm, and LOI values were 28∼31%, which indicates that the prepared AHFCs showed good flame retardancy.
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References
Akkerman, J.M., Hall, R., Mestach, D., and Vandevoorde, P.M., “Small Change,” Polym. Paint Colour J., 191, 17, 19 (2001).
Tada, M., Otsuka, I., and Oguro, K., “Two-Component Curable Polyurethane Compositions and Surface-Coated Sealing Materials Using Them,” Jpn. Patent, 363243A2 (2002).
Park, H.S., Hahm, H.S., and Park, E.K., “Preparation and Characteristics of Two-Component Polyurethane Flame Retardant Coatings Using 2,3-Dibromo Modified Polyesters,” J. Appl. Polym. Sci., 61, 421 (1996).
Park, C.H., Wu, J.P., Park, H.S., and Kim, S.K., “Syntheses and Characterizations of Two-Component Polyurethane Flame Retardant Coatings Using 2,4-Dichloro Modified Polyesters,” J. Coat. Technol., 69, 875, 41 (1997).
Nishizawa, H., The Technology and Application of Polymeric Materials: Market and Outlook, CMC Co. Ltd., Tokyo, p. 269 1996.
Ma, Z.L., Zhao, W.G., Liu, Y.F., and Shi, J.R., “Intumescent Polyurethane Coatings with Reduced Flammability Based on Spirocyclic Phosphate-Containing Polyols,” J. Appl. Polym. Sci., 66, 471 (1997).
Weil, E. and McSwigan, B., “Melamine Phosphate and Pyrophosphates in Flame Retardant Coatings,” J. Coat. Technol., 66, 839, 75 (1994).
Blount, D.H., “Flame-Retardant Polyurethane Products,” U.S. Patent 5,010,113 (1991).
Park, H.S., Kim, D.W., Dwang, K.H., Yoon, B.S., Wu, J.P., Park, J.W., Hahm, H.S., and Im, W.B., “Preparation and Characterization of Polyurethane Flame-Retardant Coatings Using Pyrophosphoric Lactone-Modified Polyesters/Isophorone Diisocyanate-Isocyanurate,” J. Appl. Polym. Sci., 80, 2316 (2001).
Park, H.S., Choi, Y.H., Kim, D.W., Im, W.B., and Wu, J.P., Fire and Polymers: Materials and Solution for Hazard Prevention, ACS Sympo. Series, Washington, D.C., Chapt. 9, pp. 110–122, 2001.
Park, H.S., Kwon, S.Y., Seo, K.J., Im, W.B., Wu, J.P., and Kim, S.K., “Preparation and Physical Properties of Polyurethane Flame Retardant Coatings Using Phosphorus-Containing Lactone Modified Polyesters,” J. Coat. Technol., 71, 899, 59 (1999).
Perrin, D.D. and Armarego, W.L.F., Purification of Laboratory Chemicals, 3rd Ed. Pergamon Press, Oxford, 1988.
Zech, J.D. and Ford, E.C., Jr., “Polyhydroxy Phosphate Esters,” U.S. Patent 3,309, 427 (1967).
Kim, H.K., Keun, J.H., Hahm, H.S., Pyoun, M.S., and Park, H.S., “Preparation of Phosphate Type Softening Flame Retardant for Synthetic Fibers and Its Characterization,” J. Korean Fiber Soc., 30, 752 (1993).
Park, C.H., Kim, S.J., Kim, Y.G., and Park, H.S., “Synthesis of Silicone Softener for Permanent Press Finish and Its Characterization,” J. Korean Oil Chem. Soc. 12, 29 (1995).
Lutz, J.T., Jr. and Grossman, R.F., Polymer Modifiers and Additives, Marcel Dekker Inc., New York, pp. 179–180, 2001.
Park, H.S., Keun, J.H., and Lee, K.S., “Syntheses and Physical Properties of Two-Component Polyurethane Flame-Retardant Coatings Using Chlorine-Containing Modified Polyesters,” J. Polym. Sci. Part A, 34, 1455 (1996).
Oldring, P.K.T. and Hayward, G., Resins for Surface Coatings, Selective Industrial Training Assoc. Ltd., London, Vol. III, pp. 109–122, 1987.
Park, H.S., Wu, J.P., and Kim, H.K., “Syntheses and Physical Properties of Two-Component Polyurethane Coatings Using Bromine-Containing Aromatic Modified Polyesters,” J. Ind. Eng. Chem. 3, 282 (1997).
Kuryla, W.C. and Papa, A.J., Flame Retardancy of Polymeric Materials, Marcel Dekker Inc., New York, Vol. 3, pp. 1–61, 1980.
Oldring, P.K.T. and Hayward, G., Resins for Surface Coatings, Selective Industrial Training Asso. Ltd., London, Vol. III, pp. 27–31, 1987.
Park, E.K., “Studies on the Syntheses and Physical Properties of Two-Component Polyurethane Flame Retardant Coatings Using Modified Aliphatic Carboxylic Acid Polyesters,” Ph.D. Dissertation, Myongji Univ., Yongin, Korea, 1994.
Grand, A.F. and Wilkie, C.A., Fire Retardancy of Polymeric Materials, Marcel Dekker Inc., New York, pp. 245–284, 2000.
Ibid., Marcel Dekker Inc., New York, pp. 147–170, 2000.
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Park, HS., You, HJ., Jo, HJ. et al. Preparation of modified polyesters containing triphosphorous and their applications to PU flame-retardant coatings. J Coat. Technol. Res. 3, 53–60 (2006). https://doi.org/10.1007/s11998-006-0005-6
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DOI: https://doi.org/10.1007/s11998-006-0005-6