Adv Polym Sci (2013) 258: 341–362
DOI: 10.1007/12_2013_223
# Springer-Verlag Berlin Heidelberg 2013
Published online: 12 June 2013
Iron Catalyst in the Preparation of Polyolefin
Composites
Robert S.A. Meyer and Gerrit A. Luinstra
Abstract The polymerization of ethylene with bis(iminoaryl)pyridyl iron precursor
is reviewed, with emphasis on the preparation of polyolefin composites by the in situ
polymerization procedure. The catalytic properties are described. The rate of the
polymerization is linearly dependent on the concentration of the active catalyst and
the ethylene concentration. Bimodal distributions arise depending on the concentration of aluminum alkyls. Aluminum alkyls are chain transfer reagents and give access
to polymeryl aluminum compounds that lead to polyethylene with a hydroxyl
terminus after oxidation with air. The bis(iminoaryl)pyridyl iron dichloride can be
supported on alumina, silica, and magnesium salts to give active catalysts after
activation with aluminum alkyls, or vice versa, that are thermally robust. The iron
complexes can also be used to prepare polyolefin (nano)composites from ethylene
after immobilization on the filler in combination with aluminum alkyls.
Keywords Aluminum alkyl Á Composite Á Ethylene polymerization Á Iron catalysis Á
Supported catalyst
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 342
1.1 Polyolefins: Polymerization and Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 342
2 Ethylene Polymerization with Iron Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 344
2.1 Combination of Aluminum Alkyls and Bis(iminoaryl)-pyridyl Iron Dichloride . . . 344
2.2 Polyethylenes from Iron Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 347
2.3 Kinetics of Polyolefin Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 348
R.S.A. Meyer and G.A. Luinstra (*)
Institut fu ¨r Technische und Makromolekulare Chemie, Fachbereich Chemie, Universita ¨t
Hamburg, 20146 Hamburg, Germany
e-mail: luinstra@chemie.uni-hamburg.de
DOI: 10.1007/12_2013_223
# Springer-Verlag Berlin Heidelberg 2013
Published online: 12 June 2013
Iron Catalyst in the Preparation of Polyolefin
Composites
Robert S.A. Meyer and Gerrit A. Luinstra
Abstract The polymerization of ethylene with bis(iminoaryl)pyridyl iron precursor
is reviewed, with emphasis on the preparation of polyolefin composites by the in situ
polymerization procedure. The catalytic properties are described. The rate of the
polymerization is linearly dependent on the concentration of the active catalyst and
the ethylene concentration. Bimodal distributions arise depending on the concentration of aluminum alkyls. Aluminum alkyls are chain transfer reagents and give access
to polymeryl aluminum compounds that lead to polyethylene with a hydroxyl
terminus after oxidation with air. The bis(iminoaryl)pyridyl iron dichloride can be
supported on alumina, silica, and magnesium salts to give active catalysts after
activation with aluminum alkyls, or vice versa, that are thermally robust. The iron
complexes can also be used to prepare polyolefin (nano)composites from ethylene
after immobilization on the filler in combination with aluminum alkyls.
Keywords Aluminum alkyl Á Composite Á Ethylene polymerization Á Iron catalysis Á
Supported catalyst
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 342
1.1 Polyolefins: Polymerization and Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 342
2 Ethylene Polymerization with Iron Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 344
2.1 Combination of Aluminum Alkyls and Bis(iminoaryl)-pyridyl Iron Dichloride . . . 344
2.2 Polyethylenes from Iron Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 347
2.3 Kinetics of Polyolefin Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 348
R.S.A. Meyer and G.A. Luinstra (*)
Institut fu ¨r Technische und Makromolekulare Chemie, Fachbereich Chemie, Universita ¨t
Hamburg, 20146 Hamburg, Germany
e-mail: luinstra@chemie.uni-hamburg.de