Korean Chemical Engineering Research

The Korean Institute of Chemical Engineers (한국화학공학회)
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Polyolefin Block Copolymer Thermoplastic Elastomer

폴리올레핀 블록공중합체 열가소성 탄성체

  • Koo, Chong Min (Hybrid Materials Research Center, Korea Institute of Science and Technology)
  • 구종민 (한국과학기술연구원 하이브리드연구재료센터)
  • Received : 2007.09.30
  • Accepted : 2007.11.05
  • Published : 2008.02.28
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Abstract

Polyolefin block copolymer has been taking a great deal of attention due to their great potential in polymer industry since a new metallocene catalytic method for producing polyolefin block copolymer was developed by Dow Chemicals. However, so far, there was no systematic study of olefin block copolymer. In this review, Linear polyolefin block copolymers, containing semicrystalline poly (ethylene) (E) blocks and a rubbery block as a thermoplastic elastomer, were investigated in the viewpoint of microphase separation mode, microstructure, deformation behavior, and molecular architecture.

최근 메탈로센 촉매를 통한 올레핀 합성 기술의 발달로 폴리올레핀 블록공중합체를 제조할 수 있는 기술이 개발되었으며 향후 고분자 산업에 크게 기여할 것으로 기대되고 있다. 하지만 현재까지 폴리올레핀 블록공중합체의 특성에 대한 체계적인 연구가 보고되고 있지 못한 실정이다. 본 리뷰 논문에서는 결정질의 poly(ethylene) (E) 블록과 고무질(rubbery)의 블록을 가지는 선형 폴리올레핀 블록공중합체를 통하여 폴리올레핀 블록공중합체의 열가소성 탄성체로서의 열역학적, 기계적 특성 및 분자 구조의 효과 특성 등에 관하여 살펴보고자 한다.

Keywords

Acknowledgement

Supported by : KOSEF, NSF

References

  1. Arriola, D. J., Carnahan, E. M., Hustad, P. D., Kuhlman, R. L. and Wenzel, T. T., "Catalytic Production of Olefin Block Copolymers Via Chain Shuttling Polymerization," Science, 312(5774), 714-719(2006). https://doi.org/10.1126/science.1125268
  2. Chen, H. Y., Poon, B., Chum, S. P., Dias, P., Hiltner, A. and Baer, E., "Olefin Block Copolymers as Polyolefin Blend Compatibilizer," ANTEC(2007).
  3. Wang, H., Taha, A., Chum, S. P., Hiltner, A. and Baer, E., "Comparison of Block and Random Ethylene-octene Copolymers Based on the Structure and Elastomeric Properties," ANTEC(2007).
  4. Olefin Block Copolymer Elastomer, Product Information, DOW Plastics.
  5. Holden, G. and Legge, N. R., In Thermoplastic Elastomers; 2nd Ed.; Hanser Publishers: New York, 48-69(1996).
  6. Quirk, R. P. and Morton, M., In Thermoplastic Elastomers; 2nd Ed.; Hanser Publishers: New York, 72-100(1996).
  7. Honeker, C. C. and Thomas, E. L., "Impact of Morphological Orientation in Determining Mechanical Properties in Triblock Copolymer Systems," Chemistry of Materials, 8(8), 1702-1714 (1996). https://doi.org/10.1021/cm960146q
  8. Keller, A. and Odell, J. A., In Processing, Structure and Properties of Block Copolymers; Elsevier Applied Science Publishers: London, 29-74(1985).
  9. Seguela, R. and Prudhomme, J., "Deformation Mechanism of Thermoplastic Two-phase Elastomers of Lamellar Morphology Having a High Volume Fraction of Rubbery Microphase," Macromolecules, 14(1), 197-202(1981). https://doi.org/10.1021/ma50002a041
  10. Pakula, T., Saijo, K., Kawai, H. and Hashimoto, T., "Deformation Behavior of Styrene-butadiene-styrene Triblock Copolymer with Cylindrical Morphology," Macromolecules, 18(6), 1294-1302 (1985). https://doi.org/10.1021/ma00148a044
  11. Falk, J. C. and Schlott, R. J., "Synthesis and Properties of Ethylene- butene-1 block Copolymers," Macromolecules, 4(2), 152-154 (1971). https://doi.org/10.1021/ma60020a004
  12. Mohajer, Y., Wilkes, G. L., Wang, I. C. and McGrath, J. E., "Hydrogenated Linear Block Copolymers of Butadiene and Isoprene: Effects of Variation of Composition and Sequence Architecture on Properties," Polymer, 23(10), 1523-1535(1982). https://doi.org/10.1016/0032-3861(82)90256-7
  13. Seguela, R. and Prudhomme, J., "Structural and Mechanical Properties of a Polyethylene Based Thermoplastic Elastomer," Polymer, 30(8), 1446-1455(1989). https://doi.org/10.1016/0032-3861(89)90214-0
  14. Ruokolainen, J., Fredrickson, G. H. and Kramer, E. J., "Effect of Thermal History and Microdomain Orientation on Deformation and Fracture Properties of Poly(cyclohexylethylene)-polyethylene triblock Copolymers Containing Cylindrical PE Domains," Macromolecules, 35(25), 9391-9402(2002). https://doi.org/10.1021/ma020791k
  15. Hermel, T. J., Hahn, S. F., Chaffin, K. A., Gerberich, W. W. and Bates, F. S., "Role of Molecular Architecture in Mechanical Failure of Glassy/semicrystalline Block Copolymers," Macromolecules, 36(16), 6280-6280(2003). https://doi.org/10.1021/ma030338o
  16. Mori, Y., Lim, L. S. and Bates, F. S., "Consequences of Molecular Bridging in Lamellae-forming Triblock/pentablock Copolymer Blends," Macromolecules, 36(26), 9879-9888(2003). https://doi.org/10.1021/ma035300q
  17. Lim, L. S., Harada, T., Hillmyer, M. A. and Bates, F. S., "High Strength Polyolefin Block Copolymers," Macromolecules, 37(16), 5847-5850(2004). https://doi.org/10.1021/ma048898q
  18. Koo, C. M., Wu, L. F., Lim, L. S., Mahanthappa, M. K., Hillmyer, M. A. and Bates, F. S., "Microstructure and Mechanical Properties of Semicrystalline-rubbery-semicrystalline Triblock Copolymers," Macromolecules, 38(14), 6090-6098(2005). https://doi.org/10.1021/ma0501794
  19. Koo, C. M., Hillmyer, M. A. and Bates, F. S., "Structure and Properties of Semicrystalline - rubbery Multiblock Copolymers," Macromolecules, 39(2), 667-677(2006). https://doi.org/10.1021/ma051098a
  20. Phatak, A., Lim, L. S., Reaves, C. K. and Bates, F. S., "Toughness of Glassy-Semicrystalline Multiblock Copolymers," Macromolecules, 39(18), 6221-6228(2006). https://doi.org/10.1021/ma0611319
  21. Mahanthappa, M. K., Lim, L. S., Hillmyer, M. A. and Bates, F. S., "Control of Mechanical Behavior in Polyolefin Composites: Integration of Glassy, Rubbery, and Semicrystalline Components," Macromolecules, 40(5), 1585-1593(2007). https://doi.org/10.1021/ma0617421
  22. Meier, D. J., "Theory of the Interface in Block Copolymers," Polymer Preprints, 15(1), 171-176(1974).
  23. Helfand, E., "Block Copolymer Theory. III. Statistical Mechanics of the Microdomain Structure," Macromolecules, 8(4), 552- 556(1975). https://doi.org/10.1021/ma60046a032
  24. Helfand, E. and Wasserman, Z. R., "Block Copolymer Theory. 4. Narrow Interphase Approximation," Macromolecules, 9(6), 879- 888(1976). https://doi.org/10.1021/ma60054a001
  25. Leibler, L., "Theory of Microphase Separation in Block Copolymers," Macromolecules, 13(6), 1602-1617(1980). https://doi.org/10.1021/ma60078a047
  26. Matsen, M. W. and Thompson, R. B., "Equilibrium Behavior of Symmetric ABA Triblock Copolymer melts," J. Chem. Phys., 111(15), 7139-7146(1999). https://doi.org/10.1063/1.480006
  27. Mayes, A. M. and Olvera de la Cruz, M., "Microphase Separation in Multiblock Copolymer Melts," J. Chem. Phys., 91(11), 7228-7235(1989). https://doi.org/10.1063/1.457290
  28. Hashimoto, T., Shibayama, M. and Kawai, H., "Domain-boundary Structure of Styrene-isoprene Block Copolymer Films Cast from Solution," Macromolecules, 13(5), 1237-1247(1980). https://doi.org/10.1021/ma60077a040
  29. DiMarzio, E. A., Guttman, C. M. and Hoffman, J. D., "Calculation of Lamellar Thickness in a Diblock Copolymer, one of Whose Components is Crystalline," Macromolecules, 21(5), 1194-1198 (1980).
  30. Whitmore, M. D. and Noolandi, J., "Theory of Crystallizable Block Copolymer Blends," Macromolecules, 21(5), 1482-1496(1988). https://doi.org/10.1021/ma00183a044
  31. Rangarajan, P., Register, R. A. and Fetters, L. J., "Morphology of Semicrystalline Block Copolymers of Ethylene-(ethylene-altpropylene)," Macromolecules, 26(17), 4640-4645(1993). https://doi.org/10.1021/ma00069a034
  32. Douzinas, K. C., Cohen, R. E. and Halasa, A. F., "Evaluation of Domain Spacing Scaling Laws for Semicrystalline Diblock Copolymers," Macromolecules, 24(15), 4457-4459(1991). https://doi.org/10.1021/ma00015a033
  33. Unger, R., Beyer, D. and Donth, E., "Phase Behavior in Poly(ethylene oxide-b-tert-butyl methacrylate) Block Copolymers," Polymer, 32(18), 3305-3312(1991). https://doi.org/10.1016/0032-3861(91)90532-N
  34. Douzinas, K. C. and Cohen, R. E., "Chain Folding in EBEE Semicrystalline Diblock Copolymers," Macromolecules, 25(19), 5030-5035(1992). https://doi.org/10.1021/ma00045a033
  35. Kofinas, P. and Cohen, R. E., "Morphology of Highly Textured Poly(ethylene)poly(ethylene-propylene)(E/EP) Semicrystalline Diblock Copolymers," Macromolecules, 27(11), 3002-3008(1994). https://doi.org/10.1021/ma00089a016