Clean Technology (청정기술)

The Korean Society of Clean Technology (한국청정기술학회)
권호 표지
DOI QR코드

DOI QR Code

A Study on Synthesis and Hydrolysis of the Maleated Polyethylene Wax

무수말레인산으로 그라프트된 폴리에틸렌 왁스의 중합과 가수분해에 대한 연구

  • Yu, Si-Won (Department of Chemical Engineering, Kwangwoon University) ;
  • Choi, Joong-So (Department of Chemical Engineering, Kwangwoon University) ;
  • Na, Jae-Sik (Department of Chemical Engineering, Kwangwoon University)
  • 유시원 (광운대학교 화학공학과) ;
  • 최중소 (광운대학교 화학공학과) ;
  • 나재식 (광운대학교 화학공학과)
  • Received : 2013.10.18
  • Accepted : 2013.11.15
  • Published : 2013.12.31
Download PDF
⟨ Previous Next ⟩

Abstract

In this study, Polyethylene wax, which was produced in manufacturing process of high density polyethylene was grafted with maleic anhydride (MAH). The influences of reaction parameters on the graft polymerization as well as the effect of hydrolysis of the anhydride functions were investigated. The results show that the grafting degree increased and conversion of maleic anhydride decreased with an increase in MAH monomer content. This means the highest grafting efficiency for the reaction can be met when MAH monomer content is about 15 wt%. DCP (dicumyl peroxide) and DTBP (di-tert-butyl peroxide) have been used as the initiator and the highest yield of grafting was obtained when the initiator content is about 0.5 wt%. However, It can be seen that the gel content values of this polyethylene wax grafted MAH were below 2%. It was also observed that the grafting degree increased with an increase in reaction temperature and the maximum value was reached 2 hours later. Although MAH functions grafted onto polyethylene wax were mainly in the carboxylic acid forms, some anhydride form of MAH appeared in over 5% of grafting degree. As a result of hydrolysis reaction, it was observed that the conversion of anhydride group into carboxylic acid group was reached up to 10%.

본 연구에서는 고밀도 폴리에틸렌 제조 공정에서의 부산물인 폴리에틸렌 왁스를 대상으로 무수말레인산(MAH)을 도입하여 솔루션 그라프트 반응을 수행 하였고, 반응 효율에 영향을 끼치는 반응 인자들과 MAH 기능기의 가수분해의 영향에 대해서 조사하였다. 측정 결과, MAH 단량체의 농도가 증가 할수록 그라프트 율은 증가하지만, 전환율은 감소하여 MAH 단량체의 농도가 15 wt% 정도에서 최대 효율을 나타냄을 알 수 있었다. DCP (dicumyl peroxide)와 DTBP (di-tert-butyl peroxide)를 개시제로 사용하여 농도에 따라 그라프트 반응한 결과, 약 0.5 wt%에서 그라프트 율이 최대값에 도달함을 볼 수 있었고, 가교반응은 2% 이하의 낮은 수치를 보임을 확인하였다. 반응온도에 따른 그라프트 율은 반응온도가 높아짐에 따라 증가하는 경향을 보이며, 최대 반응시간은 2 h 내외가 됨을 알 수 있었다. 폴리에틸렌 왁스에 그라프트 된 MAH 기능기는 주로 고리열린 상태로 존재하지만 그라프트 율이 5%이상에서는 고리가 닫힌 상태가 생성되었고, 이에 대한 가수분해 측정결과, 언하이드라이드(anhydride)기가 카르복실(carboxylic acid)기로 전환되는 율이 약 10% 정도로 측정되어, 저분자량 폴리에틸렌 왁스(polyethylene wax, PEW)-g-MAH 물성에 영향을 주는 인자로 여겨졌다.

Keywords

References

  1. Swogger, K. W., Ansems, P., and Chum, S., "Material Classification and Applications of New Propylene-Ethylene Copolymers," Soc. Plast. Eng., 61, 1768-1774 (2003).
  2. Chum, P. S., and Swogger, K. W., "Olefin Polymer Technologies- history and Recent Progress at the Dow Chemical Company," Prog. Polym. Sci., 33, 797-819 (2008). https://doi.org/10.1016/j.progpolymsci.2008.05.003
  3. La Mantia, F. P., and Morreale, M., "Mechanical Properties of Recycled Polyethylene Ecocomposites Filled with Natural Organic Fillers," Polym. Eng. Sci., 46, 1131-1139 (2006). https://doi.org/10.1002/pen.20561
  4. Moad, G., "The Synthesis of Polyolefin Graft Copolymers by Reactive Extrusion," Prog. Polym. Sci., 24, 81-142 (1999). https://doi.org/10.1016/S0079-6700(98)00017-3
  5. Choi, B. R., and Kim, H. C., "A Study on the Maleation of Polyethylene Wax Obtained as By-product in a High Density Polyethylene Plant," Korea Polym. J., 22, 56-63 (1998).
  6. Gaylord, N. G., Mehta, R., Kumar, V., and Tazi, M., "High Density Polyethylene-g-Maleic Anhydride Preparation in Presence of Electron Donors," J. Appl. Polym. Sci., 38, 359-371 (1989). https://doi.org/10.1002/app.1989.070380217
  7. Gaylord, N. G., Mehta, R., and Deshpande, A. B., "New advances in Polyolefins: Homogeneous Reaction of Maleic Anhydride with Low Density Polyethylene in Solution in Aromatic Hydrocarbons," Plenum Press, New York, 1993, pp. 115-120.
  8. Razavi Aghjeh, M. K., Nazokdast, H., and Assempour, H., "Parameters Affecting the Free-Radical Melt Grafting of Maleic Anhydride onto Linear Low-Density Polyethylene in an Internal Mixer," J. Appl. Polym. Sci., 99, 141-149 (2006). https://doi.org/10.1002/app.21870
  9. Tayyab, H., David, K. P., and Elizabeth, T., "Reaction of Low Molecular Weight Highly Functionalized Maleic Anhydride Grafted Polyethylene with Polyetherdiamines," J. Appl. Polym. Sci., 116, 2285-2297 (2010).
  10. Deng, J. P., Yang, W. T., and Ranby, B., "Melt-photografting Polymerization of Maleic Anhydride onto LDPE film," Eur. Polym. J., 38, 1449-1455 (2002). https://doi.org/10.1016/S0014-3057(02)00004-6
  11. Sclavons, M., Franquinet, P., Carlier, V., Verfaillie, G., Fallais, I., Legras, R., Laurent, M., and Thyrion, F. C., "Quantification of the Maleic Anhydride Grafted onto Polypropylene by Chemical and Viscosimetric Titrations, and FTIR spectroscopy," Polym. J., 41, 1989-1999 (2000). https://doi.org/10.1016/S0032-3861(99)00377-8
  12. Gaylord, N. G., and Mehta, R., "Peroxide-Catalyzed Grafting of Maleic Anhydride onto Molten Polyethylene," J. Polym. Lett. Ed., 20, 481 (1982). https://doi.org/10.1002/pol.1982.130200903
  13. Samay, G., Nagy, T., and White, J. L., "Grafting Maleic Anhydride and Comonomers onto Polyethylene," J. Appl. Polym. Sci., 56, 1423-1433 (1995). https://doi.org/10.1002/app.1995.070561105
  14. Sathe, S. N., Srinivasa Rao, G. S., and Devi, S., "Grafting of Maleic Anhydride onto Polypropylene: Synthesis and Characterization," J. Appl. Polym. Sci., 53, 239-245 (1994). https://doi.org/10.1002/app.1994.070530212
  15. Ghaemy, M., and Roohina, S., "Grafting of Maleic Anhydride on Polyethylene in a Homogeneous Medium in the Presence of Radical Initiators," Iran Polym. J., 12, 21-29 (2003).
  16. Ganzeveld, K. J., and Janssen, L. P. B. M. "The Grafting of Maleic Anhydride on High Density Polyethylene in an Extruder," Polym. Eng. Sci., 32, 467-474 (1992). https://doi.org/10.1002/pen.760320703
  17. Huang, L. P., Zhou, X. P., Cui, W., Xie, X. L., and Tong S. Y., "Maleic Anhydride-Grafted Linear Low-Density Polyethylene with Low Gel Content," Polym. Eng. Sci., 10, 673-679 (2009).
  18. Premamoy, G., Bibha, C., and Achintya, K. S., "Modification of Low Density Polyethylene by Graft Copolymerization with Some Acrylic Monomers," Polym. J., 39, 193-201 (1998). https://doi.org/10.1016/S0032-3861(97)00253-X
  19. Sclavons, M., Carlier, V., and De Roover, B., "Anhydride Content of Some Commercial PP-g-MA: FTIR and Titration," J. Appl. Polym. Sci., 62, 1205-1210 (1996). https://doi.org/10.1002/(SICI)1097-4628(19961121)62:8<1205::AID-APP10>3.0.CO;2-6

Cited by

  1. 열분해/그래프팅 연속반응에 의한 아크릴산 변성 폴리에틸렌 왁스 제조 vol.42, pp.3, 2013, https://doi.org/10.7317/pk.2018.42.3.466
  2. 스타이렌-무수말레인산 그래프트 반응에 의한 폴리에틸렌 왁스의 극성 특성 향상 vol.42, pp.4, 2013, https://doi.org/10.7317/pk.2018.42.4.539