Browse > Article
http://dx.doi.org/10.7473/EC.2019.54.4.286

Preparation of Flexible Terpolymers using Various Metallocene Catalyst/Borate Cocatalyst System and their Epoxidation  

Kim, Jung Soo (Department of Human Convergence Technology Group, Korea Institute of Industrial Technology (KITECH))
Choi, Jun (Department of Human Convergence Technology Group, Korea Institute of Industrial Technology (KITECH))
Kim, Dong Hyun (Department of Human Convergence Technology Group, Korea Institute of Industrial Technology (KITECH))
Publication Information
Elastomers and Composites / v.54, no.4, 2019 , pp. 286-293 More about this Journal
Abstract
In this study, flexible poly(ethylene-ter-1-hexene-ter-divinylbenzene) was prepared using four types of metallocene catalysts (rac-Et(Ind)2ZrCl2, rac-SiMe2(Ind)2ZrCl2, rac-SiMe2(2-Me-Ind)2ZrCl2, (C5Me5)TiCl2[O-2,6-iPr2(C6H3)]) and two types of borate catalysts (trityl tetrakisborate and dimethylanilinium tetrakisborate). The yield, catalytic activity, molecular weight, structure, composition, and thermal properties of the terpolymers prepared using the various catalysts and cocatalyst systems were evaluated. Epoxidation of the terpolymers was successfully performed and this transformation was studied by 1H NMR and FTIR.
Keywords
metallocene; borate; terpolymer; catalyst activity; epoxidation;
Citations & Related Records
연도 인용수 순위
  • Reference
1 R. B. Stuart, M. N. Suzanne, and R. T. David, "Coordination polymers", RSC publishing, Cambridge CB40WF, UK (2009).
2 F. G. Sernetz and R. Mulhaupt, "Metallocene-catalyzed ethene/styrene co-and terpolymerization with olefinic termonomers", J. Polym. Sci. Pol. Chem., 35, 13 (1997).
3 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. Pol. Chem., 39, 7 (2001).
4 G. Natta, P. Pino, G. Mazzanti, and U. Giannini, "A crystallizable organometallic complex containing titanium and aluminum", J. Am. Chem. Soc., 79, 11 (1957).
5 D. S. Breslow and N. R. Newburg, "Bis-(Cyclopentadienyl)-titanium dichloride-alkylaluminum complexes as soluble catalysts for the polymerization of ethylene", J. Am. Chem. Soc., 81, 1 (1959).   DOI
6 H. Sinn and W. Kaminsky, "Living polymers on polymerization with extremely productive ziegler catalysts", Angew. Chem. Int. Ed. Engl., 18, 99 (1980).
7 K. Weiss, U. Neugebuer, S. Blau, and H. J. Lang, "Untersuchungen von polymerisations und metathesereaktionen, einfach un zweifach dimethylsilylen-verbruckte metallocendichloride des Ti, Zr und Hf in der Ethen- und propenpolymerisation", J. Organomet. Chem., 520, 1 (1996).   DOI
8 W. J. Wang, E. Kolodka, S. Zhu, and Archie E. Hamilelec, "Continuous solution copolymerization of ethylene and octene with constrained geometry metallocene catalyst", J. Polym. Sci. Pol. Chem., 37, 15 (1999).   DOI
9 D. H. Lee, H. K. Jung, W. S. Kim, K. E. Min, L. S. Park, K. H. Seo, and S. K. Noh, "Copolymerization of ethylene and cycloolefin with metallocene Catalyst: I. Effect of Catalyst", Polym. Kor., 24, 4 (2000).
10 S. J. Park, W. J. Wang, and S. Zhu, "Continuous solution copolymerizarion of ethylene with propylene using a constrained geometry catalyst system", Macromol. Chem. Phys., 201, 16 (2000).
11 N. Naga and Y. Imanishi, "Copolymerization of ethylene and 1,7-octadiene, 1,9-decadiene with zirconocene catalysts", Macromol. Chem. Phys., 203, 15 (2002).   DOI
12 I. Kim, "Copolymerization of ethylene and 5-vinyl-2-norbornene by stereospecific metallocenes and epoxidation of the resulting copolymer", React. Funct. Polym., 49, 3 (2001).
13 L. He, B. Wang, F. Yang, Y. Li, and Z. Ma, "Featured crystallization polymorphism and memory effect in novel butene-1/1, 5-hexadiene copolymers synthesized by post-metallocene hafnium catalyst", Macromolecules, 49, 17 (2016).
14 K. Nomura, H. Fukuda, S. Katao, M. Fujiki, H. J. Kim, D. H. Kim, and I. Saeed, "Olefin polymerization by half-titanocenes containing ${\eta}^2$-pyrazolato ligands-MAO catalyst systems", Macromolecules, 44, 7 (2011).
15 C. De Rosa, O. Ruiz de Ballesteros, F. Auriemma, R. Di Girolamo, C. Scarica, G. Giusto, and I. Camurati, "Polymorphic behavior and mechanical properties of isotactic 1-butene-ethylene copolymers from metallocene catalysts", Macromolecules, 47, 13 (2014).   DOI
16 X. Wang, Y. Wang, X. Shi, J. Liu, C. Chen, and Y. Li, "Syntheses of well-defined functional isotactic polypropylenes via efficient copolymerization of propylene with ${\omega}-halo-{\alpha}-alkenes$ by post-metallocene hafnium catalyst", Macromolecules, 47, 2 (2014).   DOI
17 S. M. M. Mortazavi, H. Arabi, G. Zohuri, S. Ahmadjo, M. Nekoomanesh, and M. Ahmadi, "Copolymerization of ethylene/${\alpha}$-olefins using bis (2-phenylindenyl) zirconium dichloride metallocene catalyst: structural study of comonomer distribution", Polym. Int., 59, 9 (2010).
18 T. Sell, A. Winter, M. G. Thorn, A. Dimeska, and F. Langhauser, U.S. patent 8415492 (2013).
19 J. Y. Dong, H. Hong, and T. C. Chung, "Synthesis of linear polyolefin elastomers containing divinylbenzene units and application in cross-linking, functionalization, and graft reactions", Macromolecules, 36, 16 (2003).
20 K. L. Hubbard, J. A. Finch, and G. D. Darling, "Epoxidation of the pendant vinylbenzene groups of commercial poly(divinylbenzene-co-ethylvinylbenzene)", React. Funct. Polym., 42, 3 (1999).
21 B. C. Peoples, V. N. Dougnac, G. B. Galland, F. M. Rabagliati, and R. Quijada, "Preparation of poly (ethylene-co-dicyclopentadiene) copolymers and a study on their post-polymerization epoxidation", Polym. Bull., 70, 1 (2013).   DOI
22 H. J. Ban, K. Y. Lee, J. K. Lee, S. T. Chung, and W. S. Ahn, "Propylene epoxidation using titanium-contaning zeolite catalysts", Korean J. Chem. Eng., 44, 2 (2006).
23 S. Marathe and S. Sivaram, "Regioselective copolymerization of 5-vinyl-2-norbornene with ethylene using zirconocenemethylaluminoxane catalysts: A facile route to functional polyolefins", Macromolecules, 27, 5 (1994).   DOI
24 S. Machida, H. Shikuma, T. Tazaki, T. Tatsumi, and S. Kurokawa, U.S. patent 5608009 (1997).
25 F. Bai, X. Yang, and W. Huang, "Synthesis of narrow or monodisperse poly(divinylbenzene) microsheres by distillationprecipitation polymerization", Macromolecules, 37, 26 (2004).