Elastomers and Composites

The Rubber Society of Korea (한국고무학회)
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Effects of the Chain Length of High α-olefins on the Terpolymerization

High α-olefin의 사슬길이가 삼원공중합에 미치는 영향

  • Received : 2012.09.26
  • Accepted : 2012.10.30
  • Published : 2012.12.31
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Abstract

In this study, we synthesized poly(ethylene-ter-high ${\alpha}$-olefin-ter-p-methylstyrene) using Zr metallocene catalyst/borate type cocatalyst system. Various effects of the high ${\alpha}$-olefin (1-hexene, 1-octene, 1-decene, and 1-dodecene) were observed. The structure and composition of the terpolymers were characterized using $^{13}C$ NMR and $^1H$ NMR. Catalytic activity, polymer yield, molecular weight and molecular weight distribution were analyzed according to the chain length of high ${\alpha}$-olefin. We determined morphology, crystallinity and thermal properties of the terpolymers.

지르코늄계 메탈로센 촉매/Borate계 공촉매 시스템을 이용하여 poly(ethylene-ter-high ${\alpha}$-olefin-ter-p-methylstyrene)를 합성하였으며 이 때 사용한 high ${\alpha}$-olefin인 1-hexene, 1-octene, 1-decene, 1-dodecene의 사슬길이 변화가 삼원공중합체에 미치는 여러 가지 영향을 분석하였다. $^{13}C$ NMR과 $^1H$ NMR을 이용하여 삼원공중합체의 구조 및 조성을 확인하였고 high ${\alpha}$-olefin 사슬길이가 촉매활성도, 수율, 분자량 및 분자량분포도 등에 미치는 영향을 살펴보았다. 또한, 사슬 길이 변화에 따른 삼원공중합체의 morphology 변화, 결정화도 변화 및 열적 거동을 비교하였다.

Keywords

References

  1. Garoff. T, Iiskola E, and Sormunen P, "Transition Metals and Organometallicsas Catalysts for Olefin Polymerization", W. Kaminsky and H. Sinneds., Springer-Verlag, Berlin, 200 (1988).
  2. M. A. Villar and M. L. Ferreira, "Co- and terpolymerization of ethylene, propylene, and higher alpha-olefins with high propylene contents using metallocene catalysts", J. Polym. Sci. PartA : Polym. chem., 39, 1136 (2001). https://doi.org/10.1002/1099-0518(20010401)39:7<1136::AID-POLA1090>3.0.CO;2-5
  3. F. Fernanda, E. Nunes, and B. G. Griselda, "$^{13}Carbon$ Nuclear Magnetic Resonance of Ethylene-Propylene-1-hexene Terpolymers", J. Polym. Sci. PartA : Polym. chem., 42, 2474 (2004). https://doi.org/10.1002/pola.20097
  4. G. B. Galland. F. F. N. Escher, L. F da Silva, M.M.D. Forte, and R. Quijada, "Ethylene-propylene-${\alpha}$-olefin terpolymers, thermal and mechanical properties", J. Appl. Polym. Sci., 104, 3827 (2007). https://doi.org/10.1002/app.25972
  5. 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", J. Polym. Sci. Part A : Polym. chem., 36, 1017 (1998). https://doi.org/10.1002/(SICI)1099-0518(19980430)36:6<1017::AID-POLA16>3.0.CO;2-8
  6. P. Shinjoon, W. Wen-Jun, and Z. Shiping, "Continuous solution copolymerization of ethylene with propylene using a constrained geometry catalyst system", Macromol. Chem. Phys., 201, 2203 (2000). https://doi.org/10.1002/1521-3935(20001101)201:16<2203::AID-MACP2203>3.0.CO;2-V
  7. W. Wen-jun, K. Edward Z. Shiping, E. Archie, and Hamilelec, "Continuous solution copolymerization of ethylene and octene- 1 with constrained geometry metallocene catalyst", J. Polym. Sci. Part A : Polym. chem., 37, 2949 (1999). https://doi.org/10.1002/(SICI)1099-0518(19990801)37:15<2949::AID-POLA28>3.0.CO;2-W
  8. N. Naofumi and I. a Yukio, "Copolymerization of Ethylene and 1,7-Octadiene, 1,9-Decadiene with Zirconocene Catalysts", Macromol. Chem. Phys., 203, 2155 (2002). https://doi.org/10.1002/1521-3935(200211)203:15<2155::AID-MACP2155>3.0.CO;2-7
  9. I. Kim, Reactive & Functional Polymers, 49, 197 (2001). https://doi.org/10.1016/S1381-5148(01)00074-8
  10. N. Kotohiro, F. Hiroya, K. Shohei, Michiya, Fujiki, H. J. Kim, D. H. Kim, and S. Irfan, "Olefin Polymerization by Half-Titanocenes Containing ${\eta}$2-Pyrazolato Ligands−AO Catalyst Systems", Macromolecules., 44, 1986 (2011). https://doi.org/10.1021/ma200018z
  11. F. Forlini, E. Pinci, I. Tritto, M. Sacchi, and F. Piemontesi, "$^{13}C$ NMR Study of the Effect of Coordinating Solvents on Zirconocene-Catalyzed Propene/1-Hexene Copolymerization", Macromol. Chem. Phys., 203, 645 (2002). https://doi.org/10.1002/1521-3935(20020301)203:4<645::AID-MACP645>3.0.CO;2-W
  12. S. Graef, U. M. Wahner, R. Van, A. J. Sanderson, and R. D, "Copolymerization of propylene with higher ${\alpha}$-olefins in the presence of the syndiospecific catalyst i-Pr(Cp)(9-Flu) $ZrCl_{2}$/MAO", J. Polym. Sci. Part A : Polym. chem., 40, 128 (2002). https://doi.org/10.1002/pola.10093
  13. W. Kaminsky and Drogemuller, "Terpolymers of ethylene, propene and 1, 5-hexadiene synthesized with zirconocene/ methylaluminoxane", Macromol Rapid Commun., 11, 89 (1990). https://doi.org/10.1002/marc.1990.030110208
  14. W. Mingkwan, P. Piyasan, and 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
  15. N. Kotohiro, F. Fukuda, K. Shohei, Michiya, Fujiki, H. J. Kim, D. H. Kim, and Z. Shu, "Effect of ligand substituents in olefin polymerisation by half-sandwich titanium complexes containing monoanionic iminoimidazolidide ligands-MAO catalyst systems", Daltontrans., 40, 7842 (2011). https://doi.org/10.1039/c1dt10467e
  16. M. A, Da silva, and G. B. Galland, "Synthesis and characterization of ethylene-propylene-1-pentene terpolymers", J. Polym. Sci. Part A : Polym. chem., 46, 947 (2008). https://doi.org/10.1002/pola.22438
  17. E. Pérez, R. Benavente, R. Quijada, A. Narváez, and B. G. Galland, "Structure characterization of copolymers of ethylene and 1-octadecene", J. Polym. Sci. Part B : Polym. Phys., 38, 1440 (2000). https://doi.org/10.1002/(SICI)1099-0488(20000601)38:11<1440::AID-POLB40>3.0.CO;2-O
  18. K. T. Li, C. L. Dai, and C. W. Kuo, "Ethylene polymerization over a nano-sized silica supported $Cp_{2}ZrCl_{2}/MAO$ catalyst", Catal. Commun., 8, 1209 (2007). https://doi.org/10.1016/j.catcom.2006.11.011
  19. S. Krimm and A. V. Tobolsky, "Quantitative x-ray studies of order in amorphous and crystalline polymers. Quantitative x-ray determination of crystallinity in polyethylene", J. Polym. Sci. Part A : Polym. chem., 7, 57 (1951). https://doi.org/10.1002/pol.1951.120070105