Evaluation of Bis(imino)pyridine Iron Catalyst on Heterogeneous Ethylene Polymerization

This work deals with synthesis, characterization and evaluation of post-metallocene complexes based on silica-supported bis(imino)pyridine iron, containing amino groups in ethylene polymerizations. The reaction of these complexes and methylaluminoxane generated active species in heterogeneous ethylene polymerization. The absence of substituents at the orthoposition of the phenyl rings near the metal site was not compensated by the steric hindrance of the silica surface, negatively affecting the catalytic activity and the molar mass of the produced polymer. The catalyst C1, with the most bulkier ligand, presented the best performance, showing high catalytic activity not only in homogeneous system, but also in supported systems due to the chemical bond between the functionalized complex and the support surface, which led to polyethylene particles with good morphology, spherical tendency, filled pores and the decrease in bulk density compared to the particles produced through homogeneous catalyst.

[1]  A. Fedorov,et al.  Bridging the Gap between Industrial and Well-Defined Supported Catalysts. , 2018, Angewandte Chemie.

[2]  Z. Wang,et al.  Carbocyclic-fused N,N,N-pincer ligands as ring-strain adjustable supports for iron and cobalt catalysts in ethylene oligo-/polymerization , 2018 .

[3]  Wei Zhang,et al.  Tuning Bis(imino)pyridyl Iron‐Catalyzed Ethylene Oligomerization by Modification of MAO with p‐BrPhOH , 2018 .

[4]  S. Fujiwara,et al.  Simple Preparation of Halogen-Substituted α-Diimine Nickel Complexes Immobilized into Clay Interlayer as Catalysts for Ethylene Oligo-/Polymerization , 2017 .

[5]  E. P. Talsi,et al.  Iron-Catalyzed Enantioselective Epoxidations with Various Oxidants: Evidence for Different Active Species and Epoxidation Mechanisms , 2017 .

[6]  K. Schmidt-Rohr,et al.  Single-Site Heterogeneous Catalysts for Olefin Polymerization Enabled by Cation Exchange in a Metal-Organic Framework. , 2016, Journal of the American Chemical Society.

[7]  Rolf Mülhaupt,et al.  From Multisite Polymerization Catalysis to Sustainable Materials and All-Polyolefin Composites. , 2016, Chemical reviews.

[8]  M. Al‐harthi,et al.  Silica-supported (nBuCp)2ZrCl2: Effect of catalyst active center distribution on ethylene-1-hexene copolymerization , 2014 .

[9]  Y. Ko,et al.  Control of the molecular structure of ethylene-1-hexene copolymer by surface functionalization of SBA-15 with different compositions of amine groups , 2014 .

[10]  J. C. Chadwick,et al.  Immobilisation of homogeneous olefin polymerisation catalysts. Factors influencing activity and stability. , 2013, Dalton transactions.

[11]  Jin‐Heong Yim,et al.  Polymerization of olefins with single-site catalyst anchored on amine-functionalized surface of SBA-15 , 2012 .

[12]  H. Cramail,et al.  Polymer support of “single-site” catalysts for heterogeneous olefin polymerization , 2011 .

[13]  A. S. Araujo,et al.  Ethylene polymerization catalyzed by metallocene supported on mesoporous materials , 2008 .

[14]  S. Wanke,et al.  Influence of support friability and concentration of α‐olefins on gas‐phase ethylene polymerization over polymer‐supported metallocene/methylaluminoxane catalysts , 2007 .

[15]  A. Noels,et al.  Iron(II)–ethylene polymerization catalysts bearing 2,6-bis(imino)pyrazine ligands: Part II. Catalytic behaviour, homogeneous and heterogeneous insights , 2006 .

[16]  P. C. Thüne,et al.  Introducing a Flat Model of the Silica‐Supported Bis(imino)pyridyl Iron(II) Polyolefin Catalyst , 2006 .

[17]  Michael W. McKittrick Single-Site Olefin Polymerization Catalysts via the Molecular Design of Porous Silica , 2005 .

[18]  E. P. Talsi,et al.  Ferrous rather than ferric species are the active sites in bis(imino)pyridine iron ethylene polymerization catalysts , 2004 .

[19]  C. Ha,et al.  Preparation of silica-supported bis(imino)pyridyl iron(II) and cobalt(II) catalysts for ethylene polymerization , 2003 .

[20]  Zhi Ma,et al.  Preparation of silica‐supported late transition metal catalyst and ethylene polymerization , 2002 .

[21]  White,et al.  Oligomerisation of ethylene by bis(imino)pyridyliron and -cobalt complexes , 2000, Chemistry.

[22]  J. Dupont,et al.  Organosilicon-modified silicas as support for zirconocene catalyst , 2000 .

[23]  Keun-byoung Yoon,et al.  Polymerization of ethylene by using zirconocene catalyst anchored on silica with trisiloxane and pentamethylene spacers , 1997 .