콘 칼로리미터와 TGA를 이용한 할로겐 계통의 난연제를 첨가한 폴리프로필렌 수지의 난연성 및 열 안정성에 관한 연구

곽성복; 정찬화; 남재도; 김준형; 최미애; 공정호; Sung-Bok Kwak; Chan-Hwa Jung; Jae-Do Nam; Joon-Hyung Kim; Mi-Ae Choi; Jung-Ho Kong

Polymer(Korea), Vol.24, No.6, 777-786, November, 2000

Fire Resistance and Thermal Stability Study of Fire-Retarded Polypropylene Systems by Using Cone Calorimeter and Thermogravimetry

곽성복, 정찬화¹, 남재도 ^{1, †}, 김준형, 최미애, 공정호²

산자부 기술표준원
¹성균관대학교 고분자공학과
²한화석유화학중앙연구소

Sung-Bok Kwak, Chan-Hwa Jung¹, Jae-Do Nam^{1, †}, Joon-Hyung Kim, Mi-Ae Choi, and Jung-Ho Kong²

R&D Center for Resource Recycling, Agency for Technology and Standards of MOCIE, Kwacheon-city, Kyunggi-do 427-010, Korea
¹Department of Polymer Science and Engineering, Sung Kyun Kwan University, Suwon, Kyunggi-do 440-746, Korea
²Petrochemical Research Division of HANWHA R&D Center, 6 Shinsung-dong, Yusung-ku, Taejon 305-345, Korea

E-mail:

초록

본 연구에서는 범용 열가소성 수지인 폴리프로필렌(virgin polypropylene,VPP)과 폴리프로필렌을 주성분으로 하는 재생플라스틱의 난연성을 향상시키기 위하여, 난연제 decabromodiphenyloxide(DBDPO)와 chlorinated paraffin wax(CPW)를 혼합하여 이것들의 난연 특성을 정량적으로 비교 분석 연구하였다. 난연성 평가 측정으로 콘 칼로리미터(cone calorimeter,ASTM E1354,ISO 5660), 한계산소지수 측정(LOI,ASTM D2863,ISO 4589) 등을 사용하였고, 콘 칼로리미터를 이용하여 DBDPO와 CPW의 난연효율을 정량적으로 측정하였다. 콘 칼로리미터의 결과로 난연제의 난연효율을 측정한 결과, DBDPO가 CPW보다는 약 2배의 난연효율을 가지고 있다는 것을 확인하였고, 한계산소지수 측정 결과와 유사한 난연효율을 보임을 확인하였다. 열중량 분석(TGA)측정결과 난연제 DBDPO를 첨가하였을 때 약 30-50℃의 열분해 온도의 상승을 확인할 수 있었다.

Fire resistance and thermal stability of polypropylene composite systems were investigated by using several halogenated fire-retardants such as decabromodiphenyl oxide(DBDPO) and chlorinated paraffin wax(CPW). The fire resistance of composite systems was thoroughly examined by measuring limited oxygen index(LOI,ASTM D2863,ISO 4589) and characteristic properties of cone calorimetry(ASTM E1354,ISO 5660) heat release rates(HRR), time to ignition(TTI), total heat release(THR), effective heat of combustion(EHC), mass loss rates, etc. Comparing the cone calorimetry experimental results of the halogen flame retardants, DBDPO exhibited twice higher efficiency than CPW in polypropylene systems, and the LOI also showed similar trends to cone calorimetry. The thermo-oxidative stability of the composite systems was increased about 30-50 ℃ in thermogravimetry analysis. Collectively, the combustion, extiniction and thermally-stable characteristics of flame retardants were identified in this study.

Keywords:fire resistance;cone calorimetry;flame retardants(DBDPO;CPW);thermal stability;limited oxygen index(LOI)

[References]

Korea Plastic Cooperative Society, The Monthly Plastic Korea, 8, 115 (1994)
Hilado CJ, "Flammability Handbook for Plastics," 4th ed., Technomic Publishing Co., Pennsylvania, 1990 (1990)
Kuryla WC, Papa AJ, "Flame Retardancy of Polymeric Materials," vol. 1 ~ 4, Marcel Dekker, N.Y., 1973-1978 (1973)
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Hardy ML, Polym. Degrad. Stabil., 64, 545 (1999)
ASTM D2863-91 (1991)
ISO 4589 (1984)
Cullis CF, Hirschiler MM, Madden RG, Eur. Polym. J., 58, 493 (1992)
ASTM E1354-94 (1994)
ISO 5660-1 (1993)
Goff LJ, Polym. Eng. Sci., 33, 497 (1993)
Grand AF, Investigations of Fire Retarded Polymeric Systems., 3076-3078, ANTEC'96 (1996)
Checchin M, Cecchini C, Cellarosi B, Sam FO, Polym. Degrad. Stabil., 64, 573 (1999)
Cusack PA, Heer MS, Monk AW, Polym. Degrad. Stabil., 58, 229 (1997)
Chiu SH, Wang WK, Polymer, 39(10), 1951 (1998)
Babrauskas V, Grayson SJ, "Heat Release in Fires," Elsevier Science Publishers, New York, 1992 (1992)
Yang JC, Hamins A, Donnelly MK, Combust. Flame, 120(1-2), 61 (2000)
Li B, Polym. Degrad. Stabil., 68, 197 (2000)
Xiaoming X, Shiyuan C, Jianzone L, J. Appl. Polym. Sci., 45, 1145 (1992)
Choichiro S, Naohiro W, Akihiro S, Polym. Degrad. Stabil., 58, 171 (1997)
Levchik SV, Weil ED, Klatt M, Angew. Makromol. Chem., 264, 48 (1999)
Lizymol PP, Thomas S, Polym. Degrad. Stabil., 57, 187 (1997)
Zhu WM, Weil ED, J. Appl. Polym. Sci., 56(8), 925 (1995)
Casu A, Camino G, Zenoni R, Polym. Degrad. Stabil., 58, 297 (1997)
Baudry A, Dufay NR, Mortaigne B, Polym. Degrad. Stabil., 61, 441 (1998)
Carty P, Grant J, Metcalfe E, Appl. Organometal. Chem., 10, 101 (1996)
Horn WE, Stinson JM, Smith DRA, New Class of Metal Hydroxide Flame Retardants I: FR/SS Performance in Engineering Thermoplastics, 2020-2023, ANTEC'92 (1992)

[Referenced By]

[Related Articles]

[1] Korea Plastic Cooperative Society, The Monthly Plastic Korea, 8, 115 (1994)

[2] Hilado CJ, "Flammability Handbook for Plastics," 4th ed., Technomic Publishing Co., Pennsylvania, 1990 (1990)

[3] Kuryla WC, Papa AJ, "Flame Retardancy of Polymeric Materials," vol. 1 ~ 4, Marcel Dekker, N.Y., 1973-1978 (1973)

[4] Mok YI, HWAHAK KONGHAK, 15(4), 211 (1977)

[5] Pal G, Macskasy H, "Plastics Their Behavior in Fires," Elsevier Science Publishers, New York, 1991 (1991)

[6] Menachem L, "Recent Advances in Flame Retardancy of Polymeric Materials," vol. 4, Proceedings of 1993 Conference Sponsored by Business Communications Company, Inc., 1993 (1993)

[7] Nelsion GL, "Fire and Polymers II," American Chemical Society, Washington, DC, 1995 (1995)

[8] Nelsion GL, "Fire and Polymers," American Chemical Society, Washington, DC., 1990 (1990)

[9] Kim SJ, Polym. Sci. Technol., 6(2), 118 (1995)

[10] Hardy ML, Polym. Degrad. Stabil., 64, 545 (1999)

[11] ASTM D2863-91 (1991)

[12] ISO 4589 (1984)

[13] Cullis CF, Hirschiler MM, Madden RG, Eur. Polym. J., 58, 493 (1992)

[14] ASTM E1354-94 (1994)

[15] ISO 5660-1 (1993)

[16] Goff LJ, Polym. Eng. Sci., 33, 497 (1993)

[17] Grand AF, Investigations of Fire Retarded Polymeric Systems., 3076-3078, ANTEC'96 (1996)

[18] Checchin M, Cecchini C, Cellarosi B, Sam FO, Polym. Degrad. Stabil., 64, 573 (1999)

[19] Cusack PA, Heer MS, Monk AW, Polym. Degrad. Stabil., 58, 229 (1997)

[20] Chiu SH, Wang WK, Polymer, 39(10), 1951 (1998)

[21] Babrauskas V, Grayson SJ, "Heat Release in Fires," Elsevier Science Publishers, New York, 1992 (1992)

[22] Yang JC, Hamins A, Donnelly MK, Combust. Flame, 120(1-2), 61 (2000)

[23] Li B, Polym. Degrad. Stabil., 68, 197 (2000)

[24] Xiaoming X, Shiyuan C, Jianzone L, J. Appl. Polym. Sci., 45, 1145 (1992)

[25] Choichiro S, Naohiro W, Akihiro S, Polym. Degrad. Stabil., 58, 171 (1997)

[26] Levchik SV, Weil ED, Klatt M, Angew. Makromol. Chem., 264, 48 (1999)

[27] Lizymol PP, Thomas S, Polym. Degrad. Stabil., 57, 187 (1997)

[28] Zhu WM, Weil ED, J. Appl. Polym. Sci., 56(8), 925 (1995)

[29] Casu A, Camino G, Zenoni R, Polym. Degrad. Stabil., 58, 297 (1997)

[30] Baudry A, Dufay NR, Mortaigne B, Polym. Degrad. Stabil., 61, 441 (1998)

[31] Carty P, Grant J, Metcalfe E, Appl. Organometal. Chem., 10, 101 (1996)

[32] Horn WE, Stinson JM, Smith DRA, New Class of Metal Hydroxide Flame Retardants I: FR/SS Performance in Engineering Thermoplastics, 2020-2023, ANTEC'92 (1992)