Eco-Friendly Flame Retardant Poly(butylene terephthalate) Copolymers with Thermal Stability and Hydrolytic Resistance

Jong Min Park; Jun Young Lee; Yun Heum Park

Macromolecular Research, Vol.18, No.6, 539-544, June, 2010

DOI10.1007/s13233-010-0602-1 Export Citation

Eco-Friendly Flame Retardant Poly(butylene terephthalate) Copolymers with Thermal Stability and Hydrolytic Resistance

Jong Min Park, Jun Young Lee¹, and Yun Heum Park^{1, †}

KOLON Central Research Park, Yongin, 449-797, Korea
¹School of Chemical Engineering, Sungkyunkwan University, Suwon, 440-746, Korea

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Eco-friendly flame retardant poly(butylene terephthalate) copolymers (FR-PBTs) were synthesized with various amounts (5.5, 8, 10 and 15%) of the flame retardant, phosphorous comonomer unit, [(6-oxido-6H-dibenz <1,2>oxaphosphorin-6-yl)methyl]-methyl butanedioate (DOP-MBDA). Thermal stability was determined by TGA and the resistance to hydrolysis was examined by comparing the inherent viscosities of the polymers before and after hydrolysis in a 10 wt% aqueous NaOH solution at 130 ℃ for 8 h. Unfortunately the thermal stability and hydrolytic resistance of the copolymer decreased gradually with increasing DOP-MBDA content up to 10%. However, when the DOP-MBDA content was increased from 10 to 15% (FR-PBT-15), the thermal stability and hydrolytic resistance improved dramatically to those of the PBT homopolymer. FTIR spectroscopy showed that the ratio of the trans to gauche moiety in the copolymer chain decreased with increasing DOP-MBDA content up to 10%, whereas the ratio increased when 15% DOP-MBDA was incorporated into the polymer. The higher trans to gauche ratio suggests that crystallization may take place more readily in FR-PBT-15. In addition, FR-PBT-15 showed the highest density and degree of crystallinity among the copolymers. The improved thermal stability and resistance to hydrolysis of FR-PBT-15 was attributed to the denser stereo-stable crystal structure of the polymer.

Keywords:poly(butylene terephthalate) copolymer;phosporous flame retardant;thermal stability;hydrolytic stability

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[Related Articles]

[1] Alcan Chemicals, Plastics Additives & Compounding, 2, 24 (2000).

[2] Tai CM, Li RKY, Mater. Des., 22, 15 (2001)

[3] Edenbaum J, Plastics additive and modifiers handbook, Van Nostrand Reinhold Co., New York, 1992.

[4] Yeh JT, Hsieh SH, Cheng YC, Yang MJ, Chen KN, Polym. Degrad. Stabil., 61, 399 (1998)

[5] Day M, Suprunchuk TJ, Cooney D, Wiles DM, J. Appl. Polym. Sci., 33, 2041 (1987)

[6] Sato M, Endo S, Araki Y, Matsuoka G, Gyobu S, Takeuchi H, J. Appl. Polym. Sci., 78(5), 1134 (2000)

[7] Van Krevelen DW, J. Appl. Polym. Sci. Appl. Polym. Symp., 31, 269 (1977)

[8] Freudenberger V, Jakob F, Makromol. Chem., 105, 203 (1982)

[9] Pearce EM, Khanna YP, Raucher D, Thermal Characterization of Polymeric Materials, Academic Press, New York, 1983.

[10] Chang SJ, Chang FC, Polymer, 39(14), 3233 (1998)

[11] Granzow A, Cannelongo JF, J. Appl. Polym. Sci., 20, 689 (1976)

[12] Suebsaeng T, Wilkie CA, J. Polym. Sci. A: Polym. Chem., 22, 945 (1984)

[13] Chang SJ, Sheen YC, Chang RS, Chang FC, Polym. Degrad. Stabil., 54, 365 (1996)

[14] Wang CS, Shieh JY, Sun YM, Eur. Polym. J., 35, 1465 (1999)

[15] Faghihi K, Hajibeygi M, Shabanian M, Macromol. Res., 17(10), 739 (2009)

[16] Nguyen C, Kim J, Macromol. Res., 16(7), 620 (2008)

[17] Derouet D, Morvan F, Brosse JC, J. Appl. Polym. Sci., 62(11), 1855 (1996)

[18] Modern Plastics Encyclopedia, B-67, McGraw Hill, New York, 1995.

[19] Schryver DD, Landry SD, Reed JS, Polym. Degrad. Stabil., 64, 471 (1999)

[20] Levchik SV, Levchik GF, Balabanovich AI, Weil ED, Klatt M, Angew. Makromol. Chem., 264, 48 (1999)

[21] Levchik GF, Grigoriev YV, Balabanovich AI, Levchik SV, Klatt M, Polym. Int., 49, 1095 (2000)

[22] Park JM, Park YH, Macromol. Res., 13(2), 128 (2005)

[23] Camino G, Martinasso G, Costa L, Polym. Degrad. Stabil., 27, 285 (1990)

[24] Annakutty KS, Kishore K, Polymer, 29, 756 (1988)

[25] Sawada S, Kamiyama K, Ohgushi S, Yabuki K, J. Appl. Polym. Sci., 42, 1041 (1991)

[26] Kaito A, Nakayama K, Zubaidi, J. Appl. Polym. Sci., 45, 1203 (1992)

[27] Skoog DA, Leary JJ, Principles of Instrumental Analysis, 4th ed., Harcourt Brace College Publisher, Florida, 1992, Chap. 12.

[28] Mark JE, Eisenberg A, Graessley WW, Mandelkern L, Samulski ET, Koenig JL, Wignall GD, Physical Properties of Polymers, 2nd ed., ACS, Washington D.C., 1993, Chap. 6.

[29] Jang J, Oh JH, Moon SI, Macromolecules, 33(5), 1864 (2000)

[30] Pavia DL, Lampman GM, Kriz GS, Introduction to Spectroscopy, 2nd ed., Harcourt Brace College Publisher, Florida, 1996, Chap. 2.