Olefin Homopolymerization Catalyzed over Asymmetric and Symmetric Ni(II) Diimine Complexes

Tae Seok Seo; Dae Sik Hong; Dong Wook Jung; Hyun Yong Cho; Seong Ihl Woo

Korean Journal of Chemical Engineering, Vol.19, No.4, 622-626, July, 2002

DOI10.1007/BF02699307 Export Citation

Olefin Homopolymerization Catalyzed over Asymmetric and Symmetric Ni(II) Diimine Complexes

Tae Seok Seo^{1, 2}, Dae Sik Hong¹, Dong Wook Jung¹, Hyun Yong Cho¹, and Seong Ihl Woo^{1, †}

¹Department of Chemical and Biomolecular Engineering & Center for Ultramicrochemical Process Systems (CUPS), Korea Advanced Institute of Science and Technology, 373-1 Guseong-dong, Yuseong-gu, Daejeon 305-701, Korea
²Department of Chemical Engineering, Columbia University, New York, NY, 10027, Korea

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Symmetric and asymmetric Ni(II) diimine complexes such as 2-[(2,6-diisopropylphenylimino)methyl]pyridine nickel(II) dibromide (a), 2-[1-(2,6-diisopropylphenylimino)ethyl]pyridine nickel(II) dibromide (b) and [1,2-bis(2,6- diisopropylphenylimino)]acenaphthene nickel(II) dibromide (c) were synthesized. For olefin homopolymerization, asymmetric Ni(II) diimine complexes [(a) & (b)] were compared with symmetric system (c). Asymmetric Ni(II) diimine complexes exhibited less catalytic activity and thermal stability as well as more b-hydride elimination than a symmetric diimine complex (c). The activity of (a) was larger than that of (b), which indicates that methyl group has a contribution to the instability of catalyst by s bond vibration rather than the stabilization of the active site by electron releasing property.

Keywords:Olefin;Polymerization;Asymmetric;Ni(II) Diimine Complexes

[References]

Brintzinger HH, Fischer D, Mulhaupt R, Rieger B, Waymouth RM, Angew. Chem.-Int. Edit., 34, 1143 (1995)
Brookhart M, Killian CM, Johnson LK, Tempel DJ, "New Ni(II)-Based Catalysts for the Preparation of Polyolefins," 6th International Business Forum on Specialty Polyolefins, SPO '96, Houston (1996)
Brookhart M, Killian CM, Johnson LK, Tempel DJ, "Ni(II) Catalysts for the Polymerization and Copolymerization of Olefins: A New Generation of Polyolefins," Metcon'97: Polymers in Transition Proceedings (1997)
Cho HS, Choi KH, Choi DJ, Lee WY, Korean J. Chem. Eng., 17(2), 205 (2000)
E.I. Dupont de nemours and Company, WO Patent, 96/23010 (1996)
Han TK, Seo TS, Choi HK, Woo SI, Korean J. Chem. Eng., 16(2), 156 (1999)
Inoue Y, Itabashi Y, Chujo R, Polymer, 25, 1640 (1984)
Johnson LK, Killian CM, Brookhart M, J. Am. Chem. Soc., 117(23), 6414 (1995)
Kaminsky W, Macromol. Chem. Phys., 197, 3907 (1996)
Kaminsky W, Kulper K, Brintzinger HH, Wild FRWP, Angew. Chem.-Int. Edit., 24, 507 (1985)
Killian CM, Johnson LK, Brookhart M, Organometallics, 16, 2005 (1997)
Kim SH, Tewell CR, Somorjai GA, Korean J. Chem. Eng., 19(1), 1 (2002)
Koten GV, Vrieze K, Adv. Organomet. Chem., 12, 151 (1982)
Li F, Yap GPA, Scott S, Woo SI, Trans. Metal Chem., 26, 271 (2001)
Pellecchia C, Zambelli A, Macromol. Rapid Commun., 17, 333 (1996)
Svoboda M, Dieck HT, J. Org. Chem., 191, 321 (1980)
Usami T, Takayama S, Macromolecules, 17, 1756 (1984)
Ward GL, Inorg. Synth., 13, 154 (1972)
Yoon SC, Park JW, Jung HS, Song H, Park JT, Woo SI, J. Org. Chem., 559, 149 (1998)
Zambelli A, Locatelli P, Bajo G, Bovey FA, Macromolecules, 8, 687 (1975)

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[1] Brintzinger HH, Fischer D, Mulhaupt R, Rieger B, Waymouth RM, Angew. Chem.-Int. Edit., 34, 1143 (1995)

[2] Brookhart M, Killian CM, Johnson LK, Tempel DJ, "New Ni(II)-Based Catalysts for the Preparation of Polyolefins," 6th International Business Forum on Specialty Polyolefins, SPO '96, Houston (1996)

[3] Brookhart M, Killian CM, Johnson LK, Tempel DJ, "Ni(II) Catalysts for the Polymerization and Copolymerization of Olefins: A New Generation of Polyolefins," Metcon'97: Polymers in Transition Proceedings (1997)

[4] Cho HS, Choi KH, Choi DJ, Lee WY, Korean J. Chem. Eng., 17(2), 205 (2000)

[5] E.I. Dupont de nemours and Company, WO Patent, 96/23010 (1996)

[6] Han TK, Seo TS, Choi HK, Woo SI, Korean J. Chem. Eng., 16(2), 156 (1999)

[7] Inoue Y, Itabashi Y, Chujo R, Polymer, 25, 1640 (1984)

[8] Johnson LK, Killian CM, Brookhart M, J. Am. Chem. Soc., 117(23), 6414 (1995)

[9] Kaminsky W, Macromol. Chem. Phys., 197, 3907 (1996)

[10] Kaminsky W, Kulper K, Brintzinger HH, Wild FRWP, Angew. Chem.-Int. Edit., 24, 507 (1985)

[11] Killian CM, Johnson LK, Brookhart M, Organometallics, 16, 2005 (1997)

[12] Kim SH, Tewell CR, Somorjai GA, Korean J. Chem. Eng., 19(1), 1 (2002)

[13] Koten GV, Vrieze K, Adv. Organomet. Chem., 12, 151 (1982)

[14] Li F, Yap GPA, Scott S, Woo SI, Trans. Metal Chem., 26, 271 (2001)

[15] Pellecchia C, Zambelli A, Macromol. Rapid Commun., 17, 333 (1996)

[16] Svoboda M, Dieck HT, J. Org. Chem., 191, 321 (1980)

[17] Usami T, Takayama S, Macromolecules, 17, 1756 (1984)

[18] Ward GL, Inorg. Synth., 13, 154 (1972)

[19] Yoon SC, Park JW, Jung HS, Song H, Park JT, Woo SI, J. Org. Chem., 559, 149 (1998)

[20] Zambelli A, Locatelli P, Bajo G, Bovey FA, Macromolecules, 8, 687 (1975)