3 Summary, Conclusions, Outlook
The catalytic properties of BIP FeCl 2 and the options for preparation of various
polyolefins, from low molecular weight aluminum polymeryls to low molecular
weight 1-olefins for copolymerization to UHMWPE and mixtures, are presented.
The catalysts are easily prepared and can be handled in air. The activities in combination with MAO, and more conveniently with aluminum alkyls, are of the highest level
known for polyolefin formation. These catalyst are suitable for support on various
inorganic carriers in a simple procedure to become thermally more robust catalysts,
leading to the option of polymerizing ethylene at commercially relevant temperatures.
The supported catalysts have about the same catalytic properties as the homogenous
complexes and can lead to bimodally distributed products. Control over the molecular
weight distribution can be reached by tuning the ligand and, more simply, the
concentration of the cocatalysts. Hydrogen does not influence the molecular weight,
but may improve the activity to some extent. The kinetics appear to be simple: the rate
of ethylene consumption is linearly dependent on the concentration of active catalyst
and on the ethylene pressure (concentration).
Polyolefin composites are likewise easily prepared by in situ polymerizations with
the iron catalyst, i.e., after immobilization of BIP FeCl 2 complexes on the surface and
activation with aluminum alkyls (including) MAO or by aluminum alkyl-coated filler
and addition of the BIP FeCl 2 complex. The catalyst system of BIP FeCl 2 /aluminum
alkyl gives access to polymeryl aluminum compounds. The latter can be oxidized with
air to yield polyethylene alkoxides or alcohols. Such compounds may prove interesting
compounds for increasing the surface tension of polyethylene and are thus of importance, particularly for stabilizing the dispersion of inorganic nanoparticular fillers.
References
1. Hogan JP, Banks RL (1954) Polymers and production thereof. US Patent 2,825,721
2. Ziegler K, Breil H, Holzkamp E, Martin H (1953) Polymerization of ethylene. DE Patent
973,626 and (1954) US Patent 3,257,332
3. McDaniel MP (2009) Review of Phillips chromium catalyst for ethylene polymerisation.
In: Hoff R, Mathers RT (eds) Handbook of transition metal catalysts. Wiley, Hoboken
4. Wu L, Wanke SE (2009) MgCl 2 -Supported TiCl 4 catalysts for production of morphologycontrolled polyethylene. In: Hoff R, Mathers RT (eds) Handbook of transition metal catalysts.
Wiley, Hoboken
5. Yan XW, Wang J-D, Yang Y-R (2005) Polyethylene/clay nanocomposite: review of the
synthetic routes and material properties. Cailiao Kexue Yu Gongcheng Xuebao 23(1):133–136
6. Ray SS, Okamoto M (2003) Polymer/layered silicate nanocomposites: a review from preparation to processing. Prog Polym Sci 28:1539–1641
7. Jones RF (1968) Filled and reinforced polyolefins. J Petrol Sci Eng 24(8):71–74
8. Nwabunma D, Tyu W (2008) Polyolefin composites. Wiley, Hoboken
9. Guo N, DiBenedetto SA, Tewari P, Lanagan MT, Ratner MA, Marks TJ (2010) Nanoparticle, size,
shape and interfacial effects on leakage current density, permittivity, and breakdown strength of
metal oxide-polyolefin nanocomposites: experiments and theory. Chem Mater 22:1567–1578
10. Alexandre M, Dubois P, Jerome R, Gareia-Marti M, Sun T, Garces JM, Millar DM, Kuperman
A (1999) Polyolefin nanocomposites. Patent WO 99/47598
358
R.S.A. Meyer and G.A. Luinstra
The catalytic properties of BIP FeCl 2 and the options for preparation of various
polyolefins, from low molecular weight aluminum polymeryls to low molecular
weight 1-olefins for copolymerization to UHMWPE and mixtures, are presented.
The catalysts are easily prepared and can be handled in air. The activities in combination with MAO, and more conveniently with aluminum alkyls, are of the highest level
known for polyolefin formation. These catalyst are suitable for support on various
inorganic carriers in a simple procedure to become thermally more robust catalysts,
leading to the option of polymerizing ethylene at commercially relevant temperatures.
The supported catalysts have about the same catalytic properties as the homogenous
complexes and can lead to bimodally distributed products. Control over the molecular
weight distribution can be reached by tuning the ligand and, more simply, the
concentration of the cocatalysts. Hydrogen does not influence the molecular weight,
but may improve the activity to some extent. The kinetics appear to be simple: the rate
of ethylene consumption is linearly dependent on the concentration of active catalyst
and on the ethylene pressure (concentration).
Polyolefin composites are likewise easily prepared by in situ polymerizations with
the iron catalyst, i.e., after immobilization of BIP FeCl 2 complexes on the surface and
activation with aluminum alkyls (including) MAO or by aluminum alkyl-coated filler
and addition of the BIP FeCl 2 complex. The catalyst system of BIP FeCl 2 /aluminum
alkyl gives access to polymeryl aluminum compounds. The latter can be oxidized with
air to yield polyethylene alkoxides or alcohols. Such compounds may prove interesting
compounds for increasing the surface tension of polyethylene and are thus of importance, particularly for stabilizing the dispersion of inorganic nanoparticular fillers.
References
1. Hogan JP, Banks RL (1954) Polymers and production thereof. US Patent 2,825,721
2. Ziegler K, Breil H, Holzkamp E, Martin H (1953) Polymerization of ethylene. DE Patent
973,626 and (1954) US Patent 3,257,332
3. McDaniel MP (2009) Review of Phillips chromium catalyst for ethylene polymerisation.
In: Hoff R, Mathers RT (eds) Handbook of transition metal catalysts. Wiley, Hoboken
4. Wu L, Wanke SE (2009) MgCl 2 -Supported TiCl 4 catalysts for production of morphologycontrolled polyethylene. In: Hoff R, Mathers RT (eds) Handbook of transition metal catalysts.
Wiley, Hoboken
5. Yan XW, Wang J-D, Yang Y-R (2005) Polyethylene/clay nanocomposite: review of the
synthetic routes and material properties. Cailiao Kexue Yu Gongcheng Xuebao 23(1):133–136
6. Ray SS, Okamoto M (2003) Polymer/layered silicate nanocomposites: a review from preparation to processing. Prog Polym Sci 28:1539–1641
7. Jones RF (1968) Filled and reinforced polyolefins. J Petrol Sci Eng 24(8):71–74
8. Nwabunma D, Tyu W (2008) Polyolefin composites. Wiley, Hoboken
9. Guo N, DiBenedetto SA, Tewari P, Lanagan MT, Ratner MA, Marks TJ (2010) Nanoparticle, size,
shape and interfacial effects on leakage current density, permittivity, and breakdown strength of
metal oxide-polyolefin nanocomposites: experiments and theory. Chem Mater 22:1567–1578
10. Alexandre M, Dubois P, Jerome R, Gareia-Marti M, Sun T, Garces JM, Millar DM, Kuperman
A (1999) Polyolefin nanocomposites. Patent WO 99/47598
358
R.S.A. Meyer and G.A. Luinstra