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아미노실란 표면 처리 조건이 담지메탈로센 촉매의 에틸렌 중합에 미치는 영향

Effect of Surface Treatment Condition of Aminosilane on Ethylene Polymerization of Supported Metallocene

  • Lee, Sang Yun (Department of Chemical Engineering, Kongju National University) ;
  • Lee, Jeong Suk (Department of Chemical Engineering, Kongju National University) ;
  • Ko, Young Soo (Department of Chemical Engineering, Kongju National University)
  • 투고 : 2014.08.27
  • 심사 : 2014.10.18
  • 발행 : 2015.06.01

초록

N-[3-(Trimethoxysilyl)propyl]ethylenediamine (2NS)와 $N^1$-(3-trimethoxysilylpropyl)diethylenetriamine (3NS), 3-cyanopropyltriethoxysilane(1NCy)를 실리카 표면에 grafting한 후 미반응된 화합물을 제거하기 위한 세척방법과 표면처리 온도가 촉매특성에 미치는 영향을 조사하였다. Filtering법을 이용하여 합성된 담지 촉매의 Zr 담지량이 washing법 보다 높게 측정되었으나 중합 활성은 washing법으로 합성된 담지 촉매가 filtering법으로 합성된 담지 촉매보다 높았다. 표면처리 방법과 관계없이 $SiO_2/2NS/(n-BuCp)_2ZrCl_2>SiO_2/1NCy/(n-BuCp)_2ZrCl_2>SiO_2/3NS/(n-BuCp)_2ZrCl_2$ 순의 중합활성을 보였다. 아미노실란의 실리카 표면처리 온도가 증가하면 에틸렌 중합활성도 증가하였다.

The effects of surface treatment method of unreacted N-[3-(trimethoxysilyl)propyl]ethylenediamine (2NS), $N^1$-(3-trimethoxysilylpropyl)diethylenetriamine (3NS), and 3-cyanopropyltriethoxysilane (1NCy) after grafting on the surface of silica and of the surface treatment temperature on ethylene polymerization were investigated. The Zr content of supported catalyst employing filtering method was higher than that of washing method, and the activities of supported catalysts prepared by washing method were higher than those of filtering methods significantly. Regardless of surface treatment methods the activities were in order by $SiO_2/2NS/(n-BuCp)_2ZrCl_2>SiO_2/1NCy/(n-BuCp)_2ZrCl_2>SiO_2/3NS/(n-BuCp)_2ZrCl_2$. The ethylene polymerization activity was increased as the surface treatment temperature of aminosilane on silica increased.

키워드

참고문헌

  1. Monrabal, B., Blanco, J., Nieto, J. and Soares, J. B. P., "Characterization of Homogeneous Ethylene/1-Octene Copolymers Made with a Single-Site Catalyst. CRYSTAF Analysis and Calibration," J. Polym. Sci. Part A: Polym. Chem., 37(1), 89-93(1999). https://doi.org/10.1002/(SICI)1099-0518(19990101)37:1<89::AID-POLA10>3.0.CO;2-#
  2. Stadler, F. J., "Dynamic-mechanical Behavior of Polyethylenes and Ethene-/${\alpha}$-olefin-copolymers: Part III. ${\gamma}$-relaxation," Korean J. Chem. Eng., 28(10), 2057-2063(2011). https://doi.org/10.1007/s11814-011-0080-y
  3. Lee, D.-H and Yoon, K.-K., "Polymerization of Ethylene by using Zirconocene Catalyst Anchored on Silica with Trisiloxane and Pentamethylene Spacers," Macromol. Rapid Commun. 18(5), 427-431(1997). https://doi.org/10.1002/marc.1997.030180510
  4. Ribeiro, M. R., Deffieux, A. and Portela, M. F., "Supported Metallocene Complexes for Ethylene and Propylene Polymerizations: Preparation and Activity," Ind. Eng. Chem. Res., 36(4), 1224-1237 (1997). https://doi.org/10.1021/ie960475s
  5. Westcott, S. L., Oldenburg, S. J., Lee, T. R., and Halas, N. J., "Formation and Adsorption of Clusters of Gold Nanoparticles onto Functionalized Silica Nanoparticle Surfaces," Langmuir, 14(19), 5396-5401(1998). https://doi.org/10.1021/la980380q
  6. Jal, P. K., Patel, S. and Mishra, B. K., "Chemical Modification of Silica Surface by Immobilization of Functional Groups for Extractive Concentration of Metal Ions," Talanta, 62(5), 1005-1028 (2004). https://doi.org/10.1016/j.talanta.2003.10.028
  7. Ko, Y. S., Lee, J. S., Yim, J.-H., Jeon, J.-K. and Jung, K. Y., "Influence of Nanopores of MCM-41 and SBA-15 Confining $(n-BuCp)_2ZrCl_2$ on Copolymerization of Ethylene-${\alpha}$-Olefin," J. Nanosci. Nanotechnol., 10(1), 180-185(2010). https://doi.org/10.1166/jnn.2010.1536
  8. Lee, S. Y. and Ko, Y. S., "Preparation of Single-Site Catalyst Inside the Functionalized Nanopore of Silica and Its Ethylene Polymerization," J. Nanosci. Nanotech., 13(6), 4401-4404(2013). https://doi.org/10.1166/jnn.2013.7008
  9. Lee, J. S., Yim, J. H., Jeon, J. K. and Ko, Y. S., "Polymerization of Olefins with Single-site Catalyst Anchored on Amine-functionalized Surface of SBA-15," Catal. Today, 185(1) 175-182(2012). https://doi.org/10.1016/j.cattod.2011.12.003
  10. Lee, J. S. and Ko, Y. S., "Immobilization Metallocene Inside Surface-functionalized Nanopore of Micelle-Templated Silica and its Ethylene Polymerization," Polymer (Korea), 36(1), 111-116(2012). https://doi.org/10.7317/pk.2012.36.1.111
  11. Lee, J. S. and Ko, Y. S., "Control of the Molecular Structure of Ethylene-1-hexene Copolymer by Surface Functionalization of SBA-15 with Different Compositions of Amine Groups," J. Mol. Cat. A: Chem., 386(1), 120-125(2014). https://doi.org/10.1016/j.molcata.2014.01.015

피인용 문헌

  1. Effect of MAO-modified nanoporous silica supports with single-site titanocene catalyst on ethylene polymerization vol.35, pp.4, 2018, https://doi.org/10.1007/s11814-017-0337-1