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Preparation of Novel Thermoplastic Elastomers by Graft Copolymerization using Metallocene Catalyst and Cocatalyst System
Corresponding Author(s) : Dong Hyun Kim
Asian Journal of Chemistry,
Vol. 29 No. 2 (2017): Vol 29 Issue 2
Abstract
Poly(ethylene-ter-1-decene-ter-divinylbenzene) (PEDV) is prepared using rac-Et(Ind)2ZrCl2 and dimethylanilinium tetrakis-(pentafluorophenyl)borate/triisobutylaluminum as a metallocene catalyst and a cocatalyst system, respectively. The characteristic changes of the terpolymerization product according to the varying concentration of comonomers such as 1-decene and divinylbenzene (DVB) were also studied. The structure of poly(ethylene-ter-1-decene-ter-divinylbenzene) was determined by 1H NMR and the catalytic activity of the terpolymerization was found to be over 14000 kg/mol·h. PEDV-g-poly(styrenic monomers) were prepared using various styrenic monomers such as styrene, tert-butylstyrene, a-methylstyrene and p-methylstyrene. The structure of these graft copolymers was also elucidated by 1H NMR. The differential scanning calorimetry confirmed that the prepared graft copolymers had two glass transition temperatures and a high melting temperature range (250-309 °C).
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- R. Shanks and I. Kong, Thermoplastic Elastomers, In Tech, pp. 134-154 (2012).
- W. Radke, S. Roos, H.M. Stein and A.H.E. Müller, Macromol. Symp., 101, 19 (1996).
- J.P. Kennedy, J.L. Price and K. Koshimura, Macromolecules, 24, 6567 (1991).
- E.J. Markel, W. Weng, A.J. Peacock and A.H. Dekmezian, Macromolecules, 33, 8541 (2000).
- Y. Chen, A.M. Kushner, G.A. Williams and Z. Guan, Nat. Chem., 4, 467 (2012).
- K. Satoh, D.H. Lee, K. Nagai and M. Kamigaito, Macromol. Rapid Commun., 35, 161 (2014).
- F. Jiang, Z. Wang, Y. Qiao, Z. Wang and C. Tang, Macromolecules, 46, 4772 (2013).
- D. Uhrig, R. Schlegel, R. Weidisch and J. Mays, Eur. Polym. J., 47, 560 (2011).
- W. Kaminsky and H. Sinn, Transition Metals and Organometallics as Catalysts for Olefin Polymerization, Springer-Verlag, Manasquan, NJ, USA(1988).
- W. Apisuk, N. Suzuki, H.J. Kim, D.H. Kim, B. Kitiyanan and K. Nomura, J. Polym. Sci. Part A, 51, 2565 (2013).
- D.J. Yang, H.J. Kim and D.H. Kim, Catalysts, 3, 176 (2013).
- G.B. Galland, M. Seferin, R.S. Mauler and J.H.Z. Dos Santos, Polym. Int., 48, 660 (1999).
- B. Wang, Coord. Chem. Rev., 250, 242 (2006).
- J.Y. Dong, H. Hong, H.C. Wang, S. Datta and T.C. Chung, Macromolecules, 36, 6000 (2003).
- T.W. Kim, U.R. Cho and D.H. Kim, Asian J. Chem., 25, 5297 (2013).
- G.L. Yoon, D.J. Yang, H.J. Kim, J.C. Lee, N.H. Park and D.H. Kim, Asian J. Chem., 25, 5284 (2013).
- D.H. Kim, Asian J. Chem., 25, 5267 (2013).
- M. Pitsikalis and A.F. Maroudas, Synthesis of Complex Macromolecular Architectures by Metallocene and Half-Metallocene Complexes, Transworld Research Network, Kerala, India, pp. 1-59 (2013).
- R.E. Cunningham, J. Appl. Polym. Sci., 22, 2907 (1978).
- S.L. Malhotra, P. Lessard and L.P.J. Blanchard, Macromol. Sci. Pure Appl. Chem., 15, 121 (1981).
- F.M. Rabagliati, H. Muñoz and G. Mardones, J. Chil. Chem. Soc., 55, 111 (2010).
References
R. Shanks and I. Kong, Thermoplastic Elastomers, In Tech, pp. 134-154 (2012).
W. Radke, S. Roos, H.M. Stein and A.H.E. Müller, Macromol. Symp., 101, 19 (1996).
J.P. Kennedy, J.L. Price and K. Koshimura, Macromolecules, 24, 6567 (1991).
E.J. Markel, W. Weng, A.J. Peacock and A.H. Dekmezian, Macromolecules, 33, 8541 (2000).
Y. Chen, A.M. Kushner, G.A. Williams and Z. Guan, Nat. Chem., 4, 467 (2012).
K. Satoh, D.H. Lee, K. Nagai and M. Kamigaito, Macromol. Rapid Commun., 35, 161 (2014).
F. Jiang, Z. Wang, Y. Qiao, Z. Wang and C. Tang, Macromolecules, 46, 4772 (2013).
D. Uhrig, R. Schlegel, R. Weidisch and J. Mays, Eur. Polym. J., 47, 560 (2011).
W. Kaminsky and H. Sinn, Transition Metals and Organometallics as Catalysts for Olefin Polymerization, Springer-Verlag, Manasquan, NJ, USA(1988).
W. Apisuk, N. Suzuki, H.J. Kim, D.H. Kim, B. Kitiyanan and K. Nomura, J. Polym. Sci. Part A, 51, 2565 (2013).
D.J. Yang, H.J. Kim and D.H. Kim, Catalysts, 3, 176 (2013).
G.B. Galland, M. Seferin, R.S. Mauler and J.H.Z. Dos Santos, Polym. Int., 48, 660 (1999).
B. Wang, Coord. Chem. Rev., 250, 242 (2006).
J.Y. Dong, H. Hong, H.C. Wang, S. Datta and T.C. Chung, Macromolecules, 36, 6000 (2003).
T.W. Kim, U.R. Cho and D.H. Kim, Asian J. Chem., 25, 5297 (2013).
G.L. Yoon, D.J. Yang, H.J. Kim, J.C. Lee, N.H. Park and D.H. Kim, Asian J. Chem., 25, 5284 (2013).
D.H. Kim, Asian J. Chem., 25, 5267 (2013).
M. Pitsikalis and A.F. Maroudas, Synthesis of Complex Macromolecular Architectures by Metallocene and Half-Metallocene Complexes, Transworld Research Network, Kerala, India, pp. 1-59 (2013).
R.E. Cunningham, J. Appl. Polym. Sci., 22, 2907 (1978).
S.L. Malhotra, P. Lessard and L.P.J. Blanchard, Macromol. Sci. Pure Appl. Chem., 15, 121 (1981).
F.M. Rabagliati, H. Muñoz and G. Mardones, J. Chil. Chem. Soc., 55, 111 (2010).