Korean Chemical Engineering Research

  • 제53권6호
  • /
  • Pages.709-716
  • /
  • 2015
  • /
  • 0304-128X(pISSN)
  • /
  • 2233-9558(eISSN)
한국화학공학회 (The Korean Institute of Chemical Engineers)
권호 표지
DOI QR코드

DOI QR Code

유기클레이의 선택적 분산에 의한 폴리프로필렌/아이오노머/클레이 나노복합체의 유변학 및 형태학적 특성 연구

Rheology and Morphology of PP/ionomer/clay Nancomposites Depending on Selective Dispersion of Organoclays

  • 김두현 (서울대학교 화학생물공학부) ;
  • 옥현근 (서울대학교 화학생물공학부) ;
  • 안경현 (서울대학교 화학생물공학부) ;
  • 이승종 (서울대학교 화학생물공학부)
  • Kim, Doohyun (School of Chemical and Biological Engineering, Institute of Chemical Process, Seoul National University) ;
  • Ock, Hyun Geun (School of Chemical and Biological Engineering, Institute of Chemical Process, Seoul National University) ;
  • Ahn, Kyung Hyun (School of Chemical and Biological Engineering, Institute of Chemical Process, Seoul National University) ;
  • Lee, Seung Jong (School of Chemical and Biological Engineering, Institute of Chemical Process, Seoul National University)
  • 투고 : 2015.05.26
  • 심사 : 2015.08.01
  • 발행 : 2015.12.01
PDF 다운로드
⟨ 이전 논문 다음 논문 ⟩

초록

본 연구에서는 폴리프로필렌/아이오노머/클레이 삼상 복합체에서 클레이의 분산 및 위치에 따른 복합체의 구조변화와 물성을 연구하였다. 폴리프로필렌 90 wt%, 아이오노머 10 wt%의 블렌드에 클레이를 0~10 wt% 첨가하면서 물성변화를 관찰하였다. 클레이 함량 3%이하의 복합체에서 클레이는 아이오노머 상의 내부에 존재하는 반면, 클레이 함량이 증가하면서 분산상에 클레이가 채워져 견고한 구조가 형성되며 추가적인 클레이는 계면에 존재하게 된다. 이에 따라 계면에서의 상호작용은 폴리프로필렌과 아이오노머로부터 폴리프로필렌-클레이와 아이오노머-클레이의 상호작용으로 변화하며 이에 따라 미세구조 및 유변물성이 변화한다. 복합체의 저장 모듈러스(G')는 클레이가 분산상의 내부에 존재할 때는 거의 영향을 받지 않지만 클레이가 계면에 위치하면서부터 크게 증가한다. 또한 파단면의 모폴로지 역시 클레이가 복합체의 내부에만 존재할 경우에는 분산상의 상 경계가 뚜렷하게 관찰되고 분산상의 크기가 증가하지만, 클레이가 계면에 위치할 때는 분산상의 크기가 줄어들고 파단면의 모폴로지 역시 상의 경계가 뚜렷하게 관찰되지 않는 상용화된 모폴로지를 보인다. 우리는 복합체의 유변물성의 변화를 통하여 분산상 내부구조의 변화에 따른 클레이의 위치변화와 계면에서의 상호작용의 변화를 정량화 하였다. 또한 고체상태에서의 계면 접착량 측정을 통하여 계면에서의 상호작용의 증가함에 따라 접착력이 증가하고, 미세구조상 클레이 입자가 계면에 존재할 때 결정화도가 낮아짐을 확인하였다.

In this study, structural developments of polypropylene / ionomer / clay ternary composites were investigated depending on the dispersion and localization of clay. The changes in physical properties were observed adding organoclays 1~10wt% to 90% polypropylene and 10% ionomer blends. The organoclays were localized inside of the dispersed phase under the composition of 3wt%, however, over that composition, clay particles formed stiff network structure in the dispersed phase and additional clays were localized at the interface between two phases. According to the developments of microstructure, the interaction of ternary composites changed from polypropylene-ionomer to polypropylene-ionomer and ionomer-clay which affected rheological properties. The storage modulus (G') of the composites was similar to the blends when clays were localized inside of dispersed phase but increased when clays were localized at interface. Also, the fractured morphology of the composites showed phase boundary and growing radius of dispersed phase depending on addition of fillers when clays were found inside. However, when fillers found at the interface between blends, the radius of the dispersed phase decreased and compatibilized morphology were observed. The interfacial interaction of the ternary composite was quantified depending on the structural development of dispersed phase and localization of clay particles by the rheological properties. The interaction of composites at solid state which was measured through peel adhesion strength increased by growth of interfacial interaction of each component. Furthermore, the crystallinity of the composites was decreased when the clay particles were localized at the interface.

키워드

참고문헌

  1. Wu, D., Lin, D., Zhang, J., Zhou, W., Zhang, M., Zhang, Y., Wang, D. and Lin, B., "Selective Localization of Nanofillers: Effect on Morphology and Crystallization of PLA/PCL Blends," Macromolecular Chemistry and Physics, 212(6), 613-626(2011). https://doi.org/10.1002/macp.201000579
  2. Wu, S., "Calculation of Interfacial Tension in Polymer Systems," Journal of Polymer Science Part C: Polymer Symposia, 34(1), 19-30(1971). https://doi.org/10.1002/polc.5070340105
  3. Shokoohi, S., Arefazar, A. and Naderi, G., "Compatibilized PP/EPDM/PA6 Ternary Blends: Extended Morphological Studies," Polymers for Advanced Technologies, 23(3), 418-424(2012). https://doi.org/10.1002/pat.1892
  4. Sinha Ray, S. and M. Bousmina, "Compatibilization Efficiency of Organoclay in an Immiscible Polycarbonate/Poly(methyl methacrylate) Blend," Macromolecular Rapid Communications, 26(6), 450-455(2005). https://doi.org/10.1002/marc.200400586
  5. Sinha Ray, S., Pouliot, S., Bousmina, M. and Utracki, L. A., "Role of Organically Modified Layered Silicate as an Active Interfacial Modifier in Immiscible Polystyrene/polypropylene Blends," Polymer, 45(25), 8403-8413(2004). https://doi.org/10.1016/j.polymer.2004.10.009
  6. Taguet, A., Cassagnau, P. and Lopez-Cuesta, J. M., "Structuration, Selective Dispersion and Compatibilizing Effect of (nano)fillers in Polymer Blends," Progress in Polymer Science, 39(8), 1526-1563(2014). https://doi.org/10.1016/j.progpolymsci.2014.04.002
  7. Ramsden, W., "Separation of Solids in the Surface-Layers of Solutions and 'Suspensions' (Observations on Surface-Membranes, Bubbles, Emulsions, and Mechanical Coagulation). -- Preliminary Account," Proceedings of the Royal Society of London, 72, 156-164(1903). https://doi.org/10.1098/rspl.1903.0034
  8. Pickering, S. U., "CXCVI.-Emulsions," Journal of the Chemical Society, Transactions, 91(0), 2001-2021(1907). https://doi.org/10.1039/ct9079102001
  9. Hong, J., Kim, Y., Ahn, K., Lee, S. and Kim, C., "Interfacial Tension Reduction in PBT/PE/clay Nanocomposite," Rheologica Acta, 46(4), 469-478(2007). https://doi.org/10.1007/s00397-006-0123-1
  10. Hong, J. S., Namkung, H., Ahn, K. H., Lee, S. J. and Kim, C., "The Role of Organically Modified Layered Silicate in the Breakup and Coalescence of Droplets in PBT/PE Blends," Polymer, 47(11), 3967-3975(2006). https://doi.org/10.1016/j.polymer.2006.03.077
  11. Sanchez-Valdes, S., Lopez-Quintanilla, M. L., Ramirez-Vargas, E., Medellin-Rodriguez, F. J. and Gutierrez-Rodriguez, J. M., "Effect of Ionomeric Compatibilizer on Clay Dispersion in Polyethylene/ Clay Nanocomposites," Macromolecular Materials and Engineering, 291(2), 128-136(2006). https://doi.org/10.1002/mame.200500330
  12. Lim, H., Liu, H., Ahn, K., Lee, S. and Hong, J., "Effect of Added Ionomer on Morphology and Properties of PP/organoclay Nanocomposites," Korean Journal of Chemical Engineering, 27(2), 705-715(2010). https://doi.org/10.1007/s11814-010-0104-z
  13. Liu, H., Lim, H. T., Ahn, K. H. and Lee, S. J., "Effect of Ionomer on Clay Dispersions in Polypropylene-layered Silicate Nanocomposites," Journal of Applied Polymer Science, 104(6), 4024-4034 (2007). https://doi.org/10.1002/app.26036
  14. Pandey, P., Mohanty, S. and Nayak, S. K., "Influence of Thermally Induced, Dehydroxylated Nanoclay on Polymer Nanocomposites," Korean Journal of Chemical Engineering, 31(8), 1480-1489(2014). https://doi.org/10.1007/s11814-014-0094-3
  15. Wang, Y., Zhang, Q. and Fu, Q., "Compatibilization of Immiscible Poly(propylene)/Polystyrene Blends Using Clay," Macromolecular Rapid Communications, 24(3), 231-235(2003). https://doi.org/10.1002/marc.200390026
  16. Kooshki, R. M., Ghasemi, I., Karrabi, M. and Azizi, H., "Nanocomposites Based on Polycarbonate/poly (butylene terephthalate) Blends Effects of Distribution and Type of Nanoclay on Morphological Behavior," Journal of Vinyl and Additive Technology, 19(3), 203-212(2013). https://doi.org/10.1002/vnl.21313
  17. Pukanszky, B., Tudos, F., Kolarik, J. and Lednicky, F., "Ternary Composites of Polypropylene, Elastomer, and Filler: Analysis of Phase Structure Formation," Polymer Composites, 11(2), 98-104 (1990). https://doi.org/10.1002/pc.750110205
  18. Shen, L., Lin, Y., Du, Q., Zhong, W. and Yang, Y., "Preparation and Rheology of Polyamide-6/attapulgite Nanocomposites and Studies on Their Percolated Structure," Polymer, 46(15), 5758-5766(2005). https://doi.org/10.1016/j.polymer.2005.05.040
  19. Utracki, L. A. and Kanial, M. R., "Melt Rheology of Polymer Blends," Polymer Engineering & Science, 22(2), 96-114(1982). https://doi.org/10.1002/pen.760220211
  20. Sumita, M., Tsukihi, H., Miyasaka, K. and Ishikawa, K., "Dynamic Mechanical Properties of Polypropylene Composites Filled with Ultrafine Particles," Journal of Applied Polymer Science, 29(5), 1523-1530(1984). https://doi.org/10.1002/app.1984.070290506
  21. Chen, J., Shi, Y.-Y., Yang, J.-H., Zhang, N., Huang, T. and Wang, Y., "Improving Interfacial Adhesion Between Immiscible Polymers by Carbon Nanotubes," Polymer, 54(1), 464-471(2013). https://doi.org/10.1016/j.polymer.2012.11.042
  22. Kim, B., Lee, S.-H., Lee, D., Ha, B., Park, J. and Char, K., "Crystallization Kinetics of Maleated Polypropylene/Clay Hybrids," Industrial & Engineering Chemistry Research, 43(19), 6082-6089 (2004). https://doi.org/10.1021/ie049825y