자기유화 폴리에틸렌 왁스의 합성 및 에멀젼 특성 연구

양정인; 이상준; 신지훈; 한원희; 홍민혁; 김영운; Jeongin Yang; Sangjun Lee; Jihoon Shin; Won Hee Han; Min Hyuk Hong; Young-Wun Kim

Applied Chemistry for Engineering, Vol.28, No.6, 670-678, December, 2017

DOI10.14478/ace.2017.1086 Export Citation

자기유화 폴리에틸렌 왁스의 합성 및 에멀젼 특성 연구

Synthesis and Emulsion Properties of Self-emulsifiable Polyethylene Waxes

양정인¹, 이상준¹, 신지훈^{1, 2}, 한원희³, 홍민혁³, 김영운 ^{1, 2, †}

¹한국화학연구원 탄소자원화연구소 온실가스자원화연구그룹
²과학기술연합대학원대학교 KRICT 스쿨 화학소재 및 공정 전공
³(주)라이온켐텍 연구소

Jeongin Yang¹, Sangjun Lee¹, Jihoon Shin^{1, 2}, Won Hee Han³, Min Hyuk Hong³, and Young-Wun Kim^{1, 2, †}

¹Center for Greenhouse Gas Resources, Korea Research Institute of Chemical Technology (KRICT), 141 Gajeong-ro, Yuseong-gu, Daejeon, 34114, Republic of Korea
²Department of Advanced Materials and Chemical Engineering, University of Science and Technology (UST), 217 Gajeong-ro, Yuseong-gu, Daejeon 34113, Republic of Korea
³Lion Chemtech Research Institute, 36, Daedeok-daero 1277beon-gil, Daedeok-gu, Daejeon 34303, Republic of Korea

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초록

열분해 폴리에틸렌 왁스 에멀젼을 경제적으로 제조하기 위하여 아크릴산 그라프트 폴리에틸렌 왁스를 KOH와 다양한 유화제로 비누화 반응을 행하여 자기유화 폴리에틸렌 왁스를 제조하였다. 자기유화 폴리에틸렌 왁스의 비누화 반응 정도를 FT-IR 스펙트럼으로 분석한 결과, 아크릴산 그라프트 폴리에틸렌 왁스에 함유되어 있는 카르복실산 그룹에 기인한 카르보닐 피크가 사라지고 카르복실산 염 그룹에 기인한 카르보닐 피크가 새롭게 나타나는 것을 확인함으로 써 자기유화 폴리에틸렌 왁스를 제조할 수 있었다. 자기유화특성은 자기유화 폴리에틸렌 왁스를 별도의 유화제를 사용하지 않고 에멀젼을 제조한 후 에멀젼 사이즈 및 에멀젼 안정성 결과로 평가하였다. 자기유화특성 평가결과, 에멀젼 사이즈 및 에멀젼 안정성은 유화제의 양과 유화제의 구조에 따라 차이를 나타내었다. 즉, 유화제의 양이 많고 친수성을 나타내는 에틸렌옥사이드 그룹이 많이 함유되어 있는 유화제일수록 에멀젼의 사이즈가 작게 나타났으며 에멀젼 안정성이 우수하였다. 또한, 아크릴산 그라프트 폴리에틸렌 왁스를 비누화 반응으로 개질할 때 2종의 유화제를 혼합하여 개질한 자기유화 폴리에틸렌 왁스의 에멀젼의 사이즈가 단일 유화제로 개질한 자기유화 폴리에틸렌 왁스의 에멀젼 사이즈 보다 작고 에멀젼 사이즈 분포도가 대체적으로 균일하게 나타났다. 특히, OAE-5와 LAE-15 유화제를 혼합하여 개질한 자기유화 폴리에틸렌 왁스 10 wt%를 함유한 에멀젼의 에멀젼 사이즈가 4.34 μm로 가장 우수한 에멀젼 특성을 나타내었다.

Self-emulsifiable polyethylene (PE) wax was prepared using acrylic acid grafted PE wax with potassium hydroxide and various emulsifiers for the economic production of PE wax emulsion. Modification reaction completion was confirmed that the peak from carbonyl group of acrylic acid disappeared and the new peak from carboxylic acid salts appeared in the FT-IR (Fourier transform infrared) spectrum data. Self-emulsifiable properties of the modified PE wax were investigated by the emulsion size and the stability of wax emulsion without any additional emulsifiers. According to self-emulsifiable properties, the emulsion size and stability were varied on the concentration and structure of the emulsifier. The greater emulsion concentration and hydrophilic poly(ethylene oxide) (PEO) characteristics of the emulsifier resulted in the smaller emulsion size and better emulsion stability. In addition, the use of emulsifiers mixture was more effective to obtain smaller size and uniform distribution of emulsion than that of single emulsifier in PE wax modification reaction. Especially, modified PE wax with OAE-5 and LAE-15 emulsifiers mixture shows excellent performance in terms of the smallest emulsion size (4.34 μm) and emulsion stability.

Keywords:self-emulsifiable;polyethylene-g-acrylic acid (PE-g-AA) wax;emulsion characteristics

[References]

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Carroll JR, Bradley RM, Kalmikoff AI, Surf. Coat. Int., 77, 435 (1994)
Richter E, Kiesel H, Use of polyolefin waxes as external lubricants andmold release agents in processing of plastics (Clariant GmbH, Germany) PCT WO 2001072855 (2001).
Schmalzl DM, Nowicki HD, Use of polar-modified polyolefin waxesto improve adhesion of sealants to powder coatings, (Clariant GmbH,Germany) US Patent, US 2006111492 (2006).
Napoli M, Vita RD, Immediata I, Longo P, Guerra G, Polym. Adv. Technol., 22, 458 (2011)
Singh SK, Tambe SP, Samui AB, Raja VS, Kumar D, Prog. Org. Coat., 22, 20 (2006)
Villarreal N, Pastor JM, Perera R, Rosales C, Merino JC, Macromol. Chem. Phys., 203, 238 (2002)
Moad G, Prog. Polym. Sci, 24, 81 (1999)
Robert L, Pierce R, The Printing Ink Manual, Springer Science+Business B.V., Netherlands (2012).
Paik HJ, Gaynor SG, Matyjaszewski K, Macromol. Rapid Commun., 19(1), 47 (1998)
ASTM D1986-14, Standard Test Method for Determining the Apparent Viscosity of Polyethylene Wax.
ASTM D36-14, Standard Test Method for Softening Point of Bitumen (Ring-and-Ball Apparatus).
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ISO 13320:2009, Particle size analysis - Laser diffraction methods (2009).
Lerche D, J. Dispersion Sci. Technol., 5, 699 (2002)
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Hua XY, Rosen MJ, J. Colloid Interface Sci., 90, 212 (1982)
Rosen MJ, Hua XY, J. Am. Oil Chem. Soc., 59, 582 (1982)
Rosen MJ, Zhu BY, J. Colloid Interface Sci., 99, 427 (1984)
Zhu BY, Rosen MJ, J. Colloid Interface Sci., 99, 435 (1984)
Rosen MJ, Surfactants and Interfacial Phenomena, 2nd Ed., 393-419, John Wiley & Sons, New York, USA (1989).
Rosen MJ, ACS Symp. Ser., 311, 144 (1986)
Rosen MJ, Langmuir, 7, 885 (1991)
Jost F, Leiter H, Schwuger M, J. Colloid Interface Sci., 266, 554 (1988)
Lucassen-Reynders EH, Lucassen J, Giles DJ, J. Colloid Interface Sci., 81, 150 (1981)
Lee SK, Han JW, Kim BH, Shin PG, Park SK, Lim JC, J. Korean Ind. Eng. Chem., 10(4), 537 (1999)
Bae MJ, Lim JC, J. Korean Ind. Eng. Chem., 20(1), 15 (2009)

[Related Articles]

[1] Elvers B, Ullmann’s Encyclopedia of Industrial Chemistry 5th ed, 103, vol. A28, Wiley-VCH, Weinheim, Germany (1999).

[2] Carroll JR, Bradley RM, Kalmikoff AI, Surf. Coat. Int., 77, 435 (1994)

[3] Richter E, Kiesel H, Use of polyolefin waxes as external lubricants andmold release agents in processing of plastics (Clariant GmbH, Germany) PCT WO 2001072855 (2001).

[4] Schmalzl DM, Nowicki HD, Use of polar-modified polyolefin waxesto improve adhesion of sealants to powder coatings, (Clariant GmbH,Germany) US Patent, US 2006111492 (2006).

[5] Napoli M, Vita RD, Immediata I, Longo P, Guerra G, Polym. Adv. Technol., 22, 458 (2011)

[6] Singh SK, Tambe SP, Samui AB, Raja VS, Kumar D, Prog. Org. Coat., 22, 20 (2006)

[7] Villarreal N, Pastor JM, Perera R, Rosales C, Merino JC, Macromol. Chem. Phys., 203, 238 (2002)

[8] Moad G, Prog. Polym. Sci, 24, 81 (1999)

[9] Robert L, Pierce R, The Printing Ink Manual, Springer Science+Business B.V., Netherlands (2012).

[10] Paik HJ, Gaynor SG, Matyjaszewski K, Macromol. Rapid Commun., 19(1), 47 (1998)

[11] ASTM D1986-14, Standard Test Method for Determining the Apparent Viscosity of Polyethylene Wax.

[12] ASTM D36-14, Standard Test Method for Softening Point of Bitumen (Ring-and-Ball Apparatus).

[13] ASTM D1321-16a, Standard Test Method for Needle Penetration of Petroleum Waxes.

[14] ISO 13320:2009, Particle size analysis - Laser diffraction methods (2009).

[15] Lerche D, J. Dispersion Sci. Technol., 5, 699 (2002)

[16] Sobisch T, Lerche D, Kuchler S, Chem. Preprint Arch., 6, 195 (2002)

[17] Hua XY, Rosen MJ, J. Colloid Interface Sci., 90, 212 (1982)

[18] Rosen MJ, Hua XY, J. Am. Oil Chem. Soc., 59, 582 (1982)

[19] Rosen MJ, Zhu BY, J. Colloid Interface Sci., 99, 427 (1984)

[20] Zhu BY, Rosen MJ, J. Colloid Interface Sci., 99, 435 (1984)

[21] Rosen MJ, Surfactants and Interfacial Phenomena, 2nd Ed., 393-419, John Wiley & Sons, New York, USA (1989).

[22] Rosen MJ, ACS Symp. Ser., 311, 144 (1986)

[23] Rosen MJ, Langmuir, 7, 885 (1991)

[24] Jost F, Leiter H, Schwuger M, J. Colloid Interface Sci., 266, 554 (1988)

[25] Lucassen-Reynders EH, Lucassen J, Giles DJ, J. Colloid Interface Sci., 81, 150 (1981)

[26] Lee SK, Han JW, Kim BH, Shin PG, Park SK, Lim JC, J. Korean Ind. Eng. Chem., 10(4), 537 (1999)

[27] Bae MJ, Lim JC, J. Korean Ind. Eng. Chem., 20(1), 15 (2009)