불소 성분이 포함된 PTMG-IPDI 수분산 폴리우레탄의 합성과 고온 수증기에 의한 가수분해

이선아; 김영호; Sun A Lee; Young Ho Kim

Polymer(Korea), Vol.43, No.2, 252-260, March, 2019

DOI10.7317/pk.2019.43.2.252 Export Citation

불소 성분이 포함된 PTMG-IPDI 수분산 폴리우레탄의 합성과 고온 수증기에 의한 가수분해

Synthesis of PTMG-IPDI Waterborne Polyurethanes Containing Fluorine Component and Hydrolysis with High-Temperature Water Vapor

이선아, 김영호^†

숭실대학교 유기신소재·파이버공학과

Sun A Lee, and Young Ho Kim^†

Department of Organic Materials and Fiber Engineering, Soongsil University, Seoul 06978, Korea

E-mail:

초록

수분산 폴리우레탄(WPU)의 내가수분해성을 향상시키기 위하여 불소 성분을 포함하는 F-WPU를 합성하였다. 폴리테트라메틸렌에테르글리콜(PTMG), 이소포론 디이소시아네이트(IPDI), 디메틸올부타노산과 함께 불소계 디올화합물인 Fluorolink D10-H(FDH)를 0~9 wt% 사용하여 PTMG-IPDI F-WPU를 합성하고 이를 캐스팅하여 F-WPU필름을 제조하였다. 이 F-WPU 필름들을 120 °C 의 오토클레이브에서 24시간 동안 수증기로 가수분해시킨 시료들과 가수분해 전 시료들의 물성, 친수성, 모폴로지 변화를 분석하였다. 가수분해 전의 경우 F-WPU에 포함된 FDH 함량이 많아지면 시료들의 소수성은 커지면서 파단응력은 증가하고 파단신도는 감소하였다. 이들을 120 °C 의 수증기로 가수분해시키면 가수분해 전에 비해 파단응력은 크게 감소하고 파단신도는 증가하였다. F-WPU에서 FDH 함량이 7% 이상으로 되면 가수분해 전의 파단응력과 가수분해 후의 파단응력 유지율이 모두 크게 증가하여, FDH 성분 도입이 WPU의 물성 및 내가수분해성 향상에 기여하였다.

In order to improve hydrolysis resistance of waterborne polyurethane (WPU), fluorine-component containing F-WPUs were synthesized. PTMG-IPDI F-WPU films were prepared by casting the F-WPU solutions synthesized from poly(tetramethylene ether glycol) (PTMG), isophorone diisocyanate (IPDI), dimethylol butanoic acid, and Fluorolink D10-H (FDH) up to 9 wt% as a fluorine-containing diol component. Mechanical properties, hydrophilicity, and morphologies of the F-WPU films before and after hydrolysis with water vapor at 120 °C for 24 h in an autoclave were analyzed. With increasing FDH content before hydrolysis, fracture stress of the F-WPU film increased, fracture strain decreased, and hydrophobicity increased. Water vapor hydrolysis at 120 °C resulted in serious decrease in fracture stress and increase in fracture strain. Both the fracture stress before hydrolysis and the fracture stress retention after hydrolysis of the F-WPU films increased remarkably with a FDH content of 7 wt% or more, indicating that incorporation of FDH into WPU improved mechanical properties and hydrolysis resistance.

Keywords:waterborne polyurethane;PTMG-IPDI;fluorine component;water vapor;hydrolysis resistance

[References]

Li JJ, Zheng W, Zeng WB, Zhang DQ, Peng XH, Appl. Surf. Sci., 307, 255 (2014)
Ma J, Xu Q, Gao D, Zhou J, Zhang J, Polym. Degrad. Stabil., 97, 1545 (2012)
Du H, Zhao YH, Yin N, Li QF, Wang JW, Kang MQ, Xiang HW, Wang XK, J. Appl. Polym. Sci., 110(5), 3156 (2008)
Fu H, Huang H, Wang Q, Zhang H, Chen H, J. Dispersion Sci. Technol., 30, 634 (2009)
Garcia-Pacios V, Costa V, Colera M, Martin-Martinez JM, Org. Coat., 71, 136 (2011)
Rahman MM, Chun HH, Park H, Macromol. Res., 19(1), 8 (2011)
Zhou H, Wang H, Tiana X, Zhenga K, Cheng Q, Prog. Org. Coat., 77, 1073 (2014)
Zhou LC, Li YF, Bai X, Zhao GH, J. Hazard. Mater., 167(1-3), 1106 (2009)
Sarier N, Onder E, Thermochim. Acta, 510(1-2), 113 (2010)
Kuan HC, Ma CCM, Chang WP, Yuen SM, Wu HH, Lee TM, Compos. Sci. Technol., 65, 1703 (2005)
Gurunathan T, Mohanty S, Nayak SK, RCS Adv., 5, 11524 (2015)
Xiao Y, Zhao H, Wu B. Fu X, Hu K, Zhou C, Lei J, Adv. Polym. Chem., 37, 596 (2018)
Park SH, Chung ID, Hartwig A, Kim BK, Colloids Surf. A: Physicochem. Eng. Asp., 305, 126 (2007)
Zhang P, Tian S, Fan H, Chen Y, Yan J, Prog. Org. Coat., 89, 170 (2015)
Mequanint K, Sanderson R, Eur. Polym. J., 42, 1145 (2006)
Kim HS, Kim HJ, Polym. Degrad. Stabil., 93, 1544 (2008)
Wang J, Zhang H, Miao Y, Qiao L, Wang X, Wang F, Green Chem., 18, 524 (2016)
Pathan S, Ahmad S, ACS Sustain. Chem. Eng., 4, 3062 (2016)
Lee JE, Kim HJ, Polym. Korea, 29(2), 172 (2005)
Ge Z, Zhang X, Dai J, Li W, Luo Y, Eur. Polym. J., 45, 531 (2009)
Zhao M, Li H, Wen L, Yu Z, Zhang S, Han Z, J. Appl. Polym. Sci., 133, 43357 (2016)
Mun SY, Lee HD, Kim YH, Polym. Korea, 42(3), 504 (2018)
Wu L, Guo JF, Zhao S, Polym. Bull., 74(6), 2099 (2017)
Fambri L, Pegoretti A, Kolarik J, Gavazza C, Penati A, J. Therm. Anal. Calorim., 52, 787 (1998)
Thamas V, Jayabalan M, J. Biomed. Mater. Res., 56, 144 (2001)
Socrates G, Infrared and Raman Characteristic Group Frequencies, John Wiley & Sons, New York, 2004.
da Silva GR, da Silva-Cunha A, Behar-Cohen F, Ayres E, Orefice RL, Polym. Degrad. Stabil., 95, 491 (2010)
Perez-Liminana MA, Aran-Ais F, Torro-Palau AM, Orgiles-Barcelo AC, Martin-Martinez JM, Int. J. Adhes. Adhes., 25, 507 (2005)
Ramirez M, Miller KR, Soucek MD, J. Appl. Polym. Sci., 131, 40198 (2014)
Trovati G, Ap Sanches E, Neto SC, Mascarenhas YP, Chierice GO, J. Appl. Polym. Sci., 115(1), 263 (2010)
Lu MG, Lee JY, Shim MJ, Kim SW, J. Appl. Polym. Sci., 85(12), 2552 (2002)
Mondal S, Martin D, Polym. Degrad. Stabil., 97, 1553 (2012)

[1] Li JJ, Zheng W, Zeng WB, Zhang DQ, Peng XH, Appl. Surf. Sci., 307, 255 (2014)

[2] Ma J, Xu Q, Gao D, Zhou J, Zhang J, Polym. Degrad. Stabil., 97, 1545 (2012)

[3] Du H, Zhao YH, Yin N, Li QF, Wang JW, Kang MQ, Xiang HW, Wang XK, J. Appl. Polym. Sci., 110(5), 3156 (2008)

[4] Fu H, Huang H, Wang Q, Zhang H, Chen H, J. Dispersion Sci. Technol., 30, 634 (2009)

[5] Garcia-Pacios V, Costa V, Colera M, Martin-Martinez JM, Org. Coat., 71, 136 (2011)

[6] Rahman MM, Chun HH, Park H, Macromol. Res., 19(1), 8 (2011)

[7] Zhou H, Wang H, Tiana X, Zhenga K, Cheng Q, Prog. Org. Coat., 77, 1073 (2014)

[8] Zhou LC, Li YF, Bai X, Zhao GH, J. Hazard. Mater., 167(1-3), 1106 (2009)

[9] Sarier N, Onder E, Thermochim. Acta, 510(1-2), 113 (2010)

[10] Kuan HC, Ma CCM, Chang WP, Yuen SM, Wu HH, Lee TM, Compos. Sci. Technol., 65, 1703 (2005)

[11] Gurunathan T, Mohanty S, Nayak SK, RCS Adv., 5, 11524 (2015)

[12] Xiao Y, Zhao H, Wu B. Fu X, Hu K, Zhou C, Lei J, Adv. Polym. Chem., 37, 596 (2018)

[13] Park SH, Chung ID, Hartwig A, Kim BK, Colloids Surf. A: Physicochem. Eng. Asp., 305, 126 (2007)

[14] Zhang P, Tian S, Fan H, Chen Y, Yan J, Prog. Org. Coat., 89, 170 (2015)

[15] Mequanint K, Sanderson R, Eur. Polym. J., 42, 1145 (2006)

[16] Kim HS, Kim HJ, Polym. Degrad. Stabil., 93, 1544 (2008)

[17] Wang J, Zhang H, Miao Y, Qiao L, Wang X, Wang F, Green Chem., 18, 524 (2016)

[18] Pathan S, Ahmad S, ACS Sustain. Chem. Eng., 4, 3062 (2016)

[19] Lee JE, Kim HJ, Polym. Korea, 29(2), 172 (2005)

[20] Ge Z, Zhang X, Dai J, Li W, Luo Y, Eur. Polym. J., 45, 531 (2009)

[21] Zhao M, Li H, Wen L, Yu Z, Zhang S, Han Z, J. Appl. Polym. Sci., 133, 43357 (2016)

[22] Mun SY, Lee HD, Kim YH, Polym. Korea, 42(3), 504 (2018)

[23] Wu L, Guo JF, Zhao S, Polym. Bull., 74(6), 2099 (2017)

[24] Fambri L, Pegoretti A, Kolarik J, Gavazza C, Penati A, J. Therm. Anal. Calorim., 52, 787 (1998)

[25] Thamas V, Jayabalan M, J. Biomed. Mater. Res., 56, 144 (2001)

[26] Socrates G, Infrared and Raman Characteristic Group Frequencies, John Wiley & Sons, New York, 2004.

[27] da Silva GR, da Silva-Cunha A, Behar-Cohen F, Ayres E, Orefice RL, Polym. Degrad. Stabil., 95, 491 (2010)

[28] Perez-Liminana MA, Aran-Ais F, Torro-Palau AM, Orgiles-Barcelo AC, Martin-Martinez JM, Int. J. Adhes. Adhes., 25, 507 (2005)

[29] Ramirez M, Miller KR, Soucek MD, J. Appl. Polym. Sci., 131, 40198 (2014)

[30] Trovati G, Ap Sanches E, Neto SC, Mascarenhas YP, Chierice GO, J. Appl. Polym. Sci., 115(1), 263 (2010)

[31] Lu MG, Lee JY, Shim MJ, Kim SW, J. Appl. Polym. Sci., 85(12), 2552 (2002)

[32] Mondal S, Martin D, Polym. Degrad. Stabil., 97, 1553 (2012)