Synthesis and Evaluation of Arylimino Pyridine Nickel(II) Catalysts: Influence of Substituents on Polyethylene Structure

Authors:

Luiz F. Rocha, Leonardo C. Ferreira and Maria F. Marques

Instituto de Macromoleculas Professora Eloisa Mano, Universidade Federal do Rio de Janeiro RJ, Cidade Universitaria – Centro de Tecnologia – Bloco J. POBox 68525. CEP: 21945-970 Rio de Janeiro, Brazil; fmarques@ima.ufrj.br

The asymmetric arylimino pyridine Ni(II) catalysts have been examined with different substituents including diisopropyl, diethyl, fluoro, and chloro groups. The influence of these substituents and variation of ethylene pressure on the catalytic activity, crystalline structure, as well as on thermal properties of polyethylene has been investigated. The result show that complexes with substituent alkyl groups, which provide the increased electron density on the metal center (o-diethyl and o-diisopropyl) exhibit higher activity, compared to those with electron acceptors substituents (o-fluoro and o-chloro).

homogeneous catalyst

ethylene polymerization

asymmetric catalyst

[1] Ziegler K., Holzkamp E., Breil H. and Martin H.: Angew. Chem., 1955, 67, 541.
[2] Natta G. and Corradini P.: Atti Accad. Naz Lincei, Mem., Cl. Sci. Fis. Mat. Nat., 1955, 4, 73.
[3] Natta G.: J. Polym. Sci., 1955, 16, 143.
[4] Natta G., Pino P. and Mazzanti G. : Chim. Ind., 1955, 37, 927.
[5] Brintzinger H.H., Fischer D., Mühlhaupt R., Rieger B. and Waymouth R.M.: Angew. Chem. Int. Ed. Engl., 1995, 34, 1143.
[6] Gibson V.C. and Spitzmesser S.K.: Chem. Rev., 2003, 103, 283.
[7] Wang B.: Coord. Chem. Rev., 2006, 250, 242.
[8] Johnson L.K., Killian C.M. and Brookhart M.: J. Am. Chem. Soc., 1995, 117, 6414.
[9] Mecking S., Johnson L.K., Wang L. and Brookhart M.: J. Am. Chem. Soc. 1998, 120, 888.
[10] Svejda S.A. and Brookhart M.: Organometallics, 1999, 18, 65.
[11] Schleis T., Spaniol T.P. Okuda J., Heinemann J. and Mülhaupt R.J.: Organomet. Chem., 1998, 569, 159.
[12] Wang C., Friedrich S., Younkin R.T., Li T.R., Grubbs H.R., Bansleben A.D. and Day W.M.: Organometallics, 1998, 17, 3149.
[13] McLain S.J., Feldman J., McCord E.F., Gardner K.H., Teasley M.F., Coughlin E.B. and Sweetman K.J.: Macromolecules, 1998, 31, 6705.
[14] Deng L., Woo T.K., Cavallo L., Margl P.M. and Ziegler, T.: J. Am. Chem. Soc., 1997,119, 6177.
[15] Gates D.P., Svejda S.A., Oñate E., Killian C.M., Johnson L.K., White P.S. and Brookhart M.: Macromolecules, 2000, 33, 2320.
[16] Tanner M.J., Brookhart M. and DeSimone J.M.: J. Am. Chem. Soc., 1997, 119, 7617.
[17] Ceder R.M., Muller G., Ordinas M., Font-Bardia M., Solans X.J.: Chem. Soc. Dalton Trans., 2003, 15, 3052.
[18] Paulovicova A., El-Ayaan U., Shibayama K., Morita T. and Fukuda Y.: Eur. J. Inorg. Chem., 2001, 10, 2641.
[19] Nakamoto K.: Infrared and Raman Spectra of Inorganic and Coordination Compounds, 1963, 3rd ed., Ed. Wiley and Sons, 270.
[20] Ferreira L.C., Filgueiras C.A., Visentin L.C., Bordinhao J. and Horner M.: Z. Anorg. Allg. Chem., 2008, 634, 1896.
[21] Chrissopoulou K., Altintzi I., Anastasiadis S.H., Giannelis E.P., Pitsikalis M., Hadjichristidis N. and Theophilou N.: Polymer, 2005, 46, 12440.
[22] Popeney C. and Guan Z.: Organometallics, 2005, 24, 1145.
[23] Seo T.S., Hong D.S., Jung D.W., Cho H.Y. and Woo S.I.: Korean J. Chem. Eng., 2002, 19, 622.
[24] Li K., Darkwa J., Guzei I.A. and Mapolie S.F.: J. Organomet. Chem., 2002, 660, 108.
[25] Teng H., Shi Y. and Jin X.: J. Polym. Sci. Part B. Polym. Phys., 2002, 40, 2107.