Elastomers and Composites

The Rubber Society of Korea (한국고무학회)
권호 표지
DOI QR코드

DOI QR Code

Synthesis of Terpolymers and Dependence of Their Characteristics on Types and Content of High α-olefin

  • Kim, Jung Soo (Human Convergence Technology R&D Department, Korea Institute of Industrial Technology (KITECH)) ;
  • Kim, Dong Hyun (Human Convergence Technology R&D Department, Korea Institute of Industrial Technology (KITECH))
  • Received : 2020.08.24
  • Accepted : 2020.09.01
  • Published : 2020.12.31
Download PDF
⟨ Previous Next ⟩

Abstract

Novel flexible terpolymers with a reactive moiety were synthesized by coordination polymerization with a metallocene catalyst and a cocatalyst system. C2-symmetric rac-Et(Ind)2ZrCl2 and tri-iso-butylaluminum/dimethylanilinium tetrakis (pentafluorophenyl) borate were employed as the catalyst and cocatalyst, respectively. We synthesized reactive terpolymers consisting of ethylene, a high α-olefin content (1-hexene, 1-octene, 1-decene, and 1-dodecene), and divinylbenzene. The structure and composition of the terpolymers were characterized by 1H-nuclear magnetic resonance analysis. The catalytic activity, polymer yield, molecular weight, and molecular weight distribution were measured as functions of the chain length and high content of α-olefins. Furthermore, the thermal properties and crystallinity of the terpolymers were determined by differential scanning calorimetry and wide-angle X-ray scattering.

Keywords

References

  1. W. Kaminsky and H. Sinn, "Transition metals and organometallics as catalysts for olefin polymerization", Springer Science & Business Media. (2012).
  2. T. C. Chung and H. L. Lu, "Synthesis of poly(ethylene-co-p-methylstyrene) copolymers by metallocene catalysts with constrained ligand geometry", Journal of Polymer Science Part A: Polymer Chemistry, 35, 575 (1997). https://doi.org/10.1002/(SICI)1099-0518(199702)35:3<575::AID-POLA23>3.0.CO;2-K
  3. T. C. Chung and H. L. Lu, "Kinetic and microstructure studies of poly (ethylene-co-p-methylstyrene) copolymers prepared by metallocene catalysts with constrained ligand geometry", Journal of Polymer Science Part A: Polymer Chemistry, 36, 1017 (1998). https://doi.org/10.1002/(SICI)1099-0518(19980430)36:6<1017::AID-POLA16>3.0.CO;2-8
  4. S. Park, W. J. Wang, and S. Zhu, "Continuous solution copolymerization of ethylene with propylene using a constrained geometry catalyst system", Macromolecular Chemistry and Physics, 201, 2203 (2000). https://doi.org/10.1002/1521-3935(20001101)201:16<2203::AID-MACP2203>3.0.CO;2-V
  5. R. Quijada, A. Narvaez, R. Rojas, F. M. Rabagliati, G. Barrera Galland, R. Santos Mauler, and A. Bello, "Synthesis and characterization of copolymers of ethylene and 1-octadecene using the rac-Et(Ind)2ZrCl2/MAO catalyst system", Macromolecular Chemistry and Physics, 200, 1306 (1999). https://doi.org/10.1002/(SICI)1521-3935(19990601)200:6<1306::AID-MACP1306>3.0.CO;2-4
  6. I. Kim, "Copolymerization of ethylene and 5-vinyl-2-norbornene by stereospecific metallocenes and epoxidation of the resulting copolymer", Reactive and Functional Polymers, 49(3), 197-204 (2001). https://doi.org/10.1016/S1381-5148(01)00074-8
  7. K. Nomura, H. Fukuda, S. Katao, M. Fujiki, H. J. Kim, D. H. Kim, and I. Saeed, "Olefin polymerization by half-titanocenes containing η2-pyrazolato ligands- MAO catalyst systems", Macromolecules, 44, 1986 (2011). https://doi.org/10.1021/ma200018z
  8. F. Forlini, E. Princi, I. Tritto, M. C. Sacchi, and F. Piemontesi, "13C NMR study of the effect of coordinating solvents on zirconocene-catalyzed propene/1-hexene copolymerization", Macromolecular Chemistry and Physics, 203, 645 (2002). https://doi.org/10.1002/1521-3935(20020301)203:4<645::AID-MACP645>3.0.CO;2-W
  9. W. Mingkwan and P. Piyasan, "Bunjerd, Observation of different catalytic activity of various 1-olefins during ethylene/1-olefin copolymerization with homogeneous metallocene catalysts", J. Molecules, 16, 373 (2011). https://doi.org/10.3390/molecules16010373
  10. K. Nomura, H. Fukuda, S. Katao, M. Fujiki, H. J. Kim, D. H. Kim, and S. Zhang, "Effect of ligand substituents in olefin polymerisation by half-sandwich titanium complexes containing monoanionic iminoimidazolidide ligands-MAO catalyst systems", Dalton Transactions, 40, 7842 (2011). https://doi.org/10.1039/c1dt10467e
  11. D. J. Yang, H. J. Kim, and D. H. Kim, "A Comparative Study on the homo-, co-and ter-polymerization using ethylene, 1-decene and p-methylstyrene", Catalysts, 3, 176 (2013). https://doi.org/10.3390/catal3010176
  12. H. W. Lee and Y. H. Park, "Effect of cocatalyst type on the characteristics of olefin polymerization with in-situ supported metallocene catalysts", Journal of Industrial and Engineering Chemistry, 13, 570 (2002).
  13. J. S. Yoon, D. H. Lee, E. S. Park, I. M. Lee, D. K. Park, and S. O. Jung, "Copolymerization of ethylene/α-olefins over (2-MeInd)2ZrCl2/MAO and (2-BzInd)2ZrCl2/MAO systems", Journal of Applied Polymer Science, 75, 928 (2000). https://doi.org/10.1002/(SICI)1097-4628(20000214)75:7<928::AID-APP9>3.0.CO;2-P
  14. T. W. Kim, H. K. Kim, J. C. Lee, N. H. Park, U. R. Cho, and D. H. Kim, "Effects of the chain length of high α-olefins on the terpolymerization", Elastomers and Composites, 47, 329 (2011).
  15. T. W. Kim, U. R. Cho, and D. H. Kim, "Effects of various high a-olefins on the terpolymerization with metallocene catalyst and cocatalyst system", Asian Journal of Chemistry, 25, 5297 (2013). https://doi.org/10.14233/ajchem.2013.f36