The Ethylene Polymerization with Ziegler Catalysts: Fifty Years after the Discovery

Angewandte Chemie - International Edition

Volumn 42, Issue 41, 2003, Pages 5010-5030

  Böhm, Ludwig L ^a  

^a Basell Polyolefine GmbH   (Germany)

Author keywords

Alkenes; Polyethylenes; Polymerization; Supported catalysts; Titanium; Ziegler catalysts

Indexed keywords

ALUMINUM COMPOUNDS; COSTS; POLYETHYLENES; POLYMERIZATION; PRESSURE EFFECTS;

COCATALYSTS; LOW PRESSURE EFFECTS;

CATALYST ACTIVITY;

ALKENE; ALUMINUM DERIVATIVE; CONCRETE; ETHYLENE; GLASS; ORGANIC COMPOUND; POLYETHYLENE; STEEL; TITANIUM; TRANSITION ELEMENT;

ACHIEVEMENT; CATALYSIS; CATALYST; COST CONTROL; ENVIRONMENTAL FACTOR; ENVIRONMENTAL PROTECTION; HIGH TEMPERATURE; HYPOBARISM; MATERIALS; PAPER; POLYMERIZATION; REACTION ANALYSIS; RESEARCH; REVIEW; SYNTHESIS; ZIEGLER CATALYST;

EID: 0242354911     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200300580     Document Type: Review

References (162)

1. K. Ziegler, Angew. Chem. 1964, 76, 545-553.
2. K. Ziegler, E. Holzkamp, H. Breil, H. Martin, Angew. Chem. 1955, 67, 426.
3. K. Ziegler, H. Breil, E. Holzkamp, H. Martin. DE 973 626, 1953 [Chem. Abstr. 1960, 54, 14794].
4. With these catalysts Natta and co-workers polymerized propylene to isotactic polypropylene (i-PP). They discovered the principles of the regio- and stereospecific polymerization of 1-alkenes: G. Natta, Angew. Chem. 1956, 68, 869-887; G. Natta, Angew. Chem. 1964, 76, 553-566; and references therein.
5. With these catalysts Natta and co-workers polymerized propylene to isotactic polypropylene (i-PP). They discovered the principles of the regio- and stereospecific polymerization of 1-alkenes: G. Natta, Angew. Chem. 1956, 68, 869-887; G. Natta, Angew. Chem. 1964, 76, 553-566; and references therein.
6. The process to synthesize isotactic polypropylene was again transferred into a industrial process within a few years because an new polymer (polypropylene) with new properties was accessible: A. Bosoni, G. Guzzetta, I. Ronzoni, F. Sabbioni, Mater. Plast. 1956, 12, 1010-1022; G. Lombardo, Mater. Plast. 1957, 13, 409-414; G. Ballabio, Mater. Plast. 1957, 13, 415-419; R. Pozzo, S. Compostella, Mater. Plast. 1957, 13, 425-434.
7. The process to synthesize isotactic polypropylene was again transferred into a industrial process within a few years because an new polymer (polypropylene) with new properties was accessible: A. Bosoni, G. Guzzetta, I. Ronzoni, F. Sabbioni, Mater. Plast. 1956, 12, 1010-1022; G. Lombardo, Mater. Plast. 1957, 13, 409-414; G. Ballabio, Mater. Plast. 1957, 13, 415-419; R. Pozzo, S. Compostella, Mater. Plast. 1957, 13, 425-434.
8. The process to synthesize isotactic polypropylene was again transferred into a industrial process within a few years because an new polymer (polypropylene) with new properties was accessible: A. Bosoni, G. Guzzetta, I. Ronzoni, F. Sabbioni, Mater. Plast. 1956, 12, 1010-1022; G. Lombardo, Mater. Plast. 1957, 13, 409-414; G. Ballabio, Mater. Plast. 1957, 13, 415-419; R. Pozzo, S. Compostella, Mater. Plast. 1957, 13, 425-434.
9. The process to synthesize isotactic polypropylene was again transferred into a industrial process within a few years because an new polymer (polypropylene) with new properties was accessible: A. Bosoni, G. Guzzetta, I. Ronzoni, F. Sabbioni, Mater. Plast. 1956, 12, 1010-1022; G. Lombardo, Mater. Plast. 1957, 13, 409-414; G. Ballabio, Mater. Plast. 1957, 13, 415-419; R. Pozzo, S. Compostella, Mater. Plast. 1957, 13, 425-434.
10. These catalysts can also be used for the copolymerization of ethylene and propylene to produce ethylene-propylene elastomers; again these were new polymers: G. Crespi, A. Valvassori, G. Sartori in High Polymers, Vol. 18 (Ed.: G. E. Ham), Wiley-Interscience, New York, 1964, pp. 231-274.
11. E. W. Fawcett, R. U. Gibson, M. W. Perrin, J. G. Paton, E. G. Williams (ICI), GB 471590, 1936 [Chem. Abstr, 1938, 32, 1362]; Polyethylenes 1933-1983: Past, Present, Future. The Plastics and Rubber Institute, London, 1983.
12. E. W. Fawcett, R. U. Gibson, M. W. Perrin, J. G. Paton, E. G. Williams (ICI), GB 471590, 1936 [Chem. Abstr, 1938, 32, 1362]; Polyethylenes 1933-1983: Past, Present, Future. The Plastics and Rubber Institute, London, 1983.
13. In the first Hostalen brochure [Ed. Farbwerke Hoechst AG, 1956] the introduction states: "The properties are in part very different compared to polyethylenes produced with the high-pressure process". This point was stressed in further publications: K. Ziegler, Angew. Chem. 1955, 67, 541-547; E. Grams, E. Gaube, Angew. Chem. 1955, 67, 548-556; G. Schulz, K. Mehnert, Kunststoffe 1955, 45, 410-414; Kunststoff-Praxis 1955, 12, P101-P107; W. Kneip, Chem. Ind. 1955, 7, 297-298.
14. In the first Hostalen brochure [Ed. Farbwerke Hoechst AG, 1956] the introduction states: "The properties are in part very different compared to polyethylenes produced with the high-pressure process". This point was stressed in further publications: K. Ziegler, Angew. Chem. 1955, 67, 541-547; E. Grams, E. Gaube, Angew. Chem. 1955, 67, 548-556; G. Schulz, K. Mehnert, Kunststoffe 1955, 45, 410-414; Kunststoff-Praxis 1955, 12, P101-P107; W. Kneip, Chem. Ind. 1955, 7, 297-298.
15. In the first Hostalen brochure [Ed. Farbwerke Hoechst AG, 1956] the introduction states: "The properties are in part very different compared to polyethylenes produced with the high-pressure process". This point was stressed in further publications: K. Ziegler, Angew. Chem. 1955, 67, 541-547; E. Grams, E. Gaube, Angew. Chem. 1955, 67, 548-556; G. Schulz, K. Mehnert, Kunststoffe 1955, 45, 410-414; Kunststoff-Praxis 1955, 12, P101-P107; W. Kneip, Chem. Ind. 1955, 7, 297-298.
16. In the first Hostalen brochure [Ed. Farbwerke Hoechst AG, 1956] the introduction states: "The properties are in part very different compared to polyethylenes produced with the high-pressure process". This point was stressed in further publications: K. Ziegler, Angew. Chem. 1955, 67, 541-547; E. Grams, E. Gaube, Angew. Chem. 1955, 67, 548-556; G. Schulz, K. Mehnert, Kunststoffe 1955, 45, 410-414; Kunststoff-Praxis 1955, 12, P101-P107; W. Kneip, Chem. Ind. 1955, 7, 297-298.
17. In the first Hostalen brochure [Ed. Farbwerke Hoechst AG, 1956] the introduction states: "The properties are in part very different compared to polyethylenes produced with the high-pressure process". This point was stressed in further publications: K. Ziegler, Angew. Chem. 1955, 67, 541-547; E. Grams, E. Gaube, Angew. Chem. 1955, 67, 548-556; G. Schulz, K. Mehnert, Kunststoffe 1955, 45, 410-414; Kunststoff-Praxis 1955, 12, P101-P107; W. Kneip, Chem. Ind. 1955, 7, 297-298.
18. In the first Hostalen brochure [Ed. Farbwerke Hoechst AG, 1956] the introduction states: "The properties are in part very different compared to polyethylenes produced with the high-pressure process". This point was stressed in further publications: K. Ziegler, Angew. Chem. 1955, 67, 541-547; E. Grams, E. Gaube, Angew. Chem. 1955, 67, 548-556; G. Schulz, K. Mehnert, Kunststoffe 1955, 45, 410-414; Kunststoff-Praxis 1955, 12, P101-P107; W. Kneip, Chem. Ind. 1955, 7, 297-298.
19. This polymerization process was transferred into a industrial process which was the same as the laboratory-scale procass. As early as the end of 1955 the production was on stream E. Bäumler, Farben, Formen, Forscher, Hoechst und die Geschichte der industriellen Chemie in Deutschland, Piper, München, 1989, pp. 335-340.
20. This new process was seen as a technological breakthrough, and therefore it was presented at the world exhibition at Brussels in 1958. The visitors could see how gaseous ethylene was converted into a white powder, and how this powder was molten and injection molded into a badge which they could take with them: S. Sommer, S. Wagener, H. Ebner, Kunststoffe 1959, 49, 500-502; this plant was presented to Deutsches Museum at München after the world exhibition.
21. The catalysts discovered by Ziegler and co-workers and further developed in industry show a catalyst productivity in the range below 5 kg polyethylene per g of titanium: B. Diedrich, Appl. Polym. Symp. 1975, 26, 1-11; The catalyst used today achieve values of 100 kg polyethylene per g titanium. Catalyst productivity means the amount (mass) of polyethylene in kg related to the amount (mass) of catalyst in g titanium under industrial reaction conditions of temperature, ethylene partial pressure, average residence time, space time yield, and others. This value is thus a number for the catalyst activity under well-defined industrial process conditions. With this number the performance of catalysts can be compared.
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28. K. S. Whiteley, T. G. Heggs, H. Koch, R. L. Mawer, W. Immel in Ullmann's Encyclopedia of Industrial Chemistry, Vol. A21, VCH, Weinheim, 1992, pp. 487-577; and references therein.
29. 3 (α, β, γ, δ). For all modifications the chlorine ions form a spherical close packaging. The different modifications follow from the different arrangement of the chlorine-ion layers. The δ modification is the preferred one for catalysts. In this case the layers are random. For the α and γ modification the layers are periodic. The β modification has another structure: G. Natta, P. Corradini, G. Allegra, J. Polym. Sci. 1961, 51, 399-410; T. Keii, Kinetics of Ziegler-Natta Polymerzation, Kodansha, Tokyo, 1972, pp. 44-45.
30. 3 (α, β, γ, δ). For all modifications the chlorine ions form a spherical close packaging. The different modifications follow from the different arrangement of the chlorine-ion layers. The δ modification is the preferred one for catalysts. In this case the layers are random. For the α and γ modification the layers are periodic. The β modification has another structure: G. Natta, P. Corradini, G. Allegra, J. Polym. Sci. 1961, 51, 399-410; T. Keii, Kinetics of Ziegler-Natta Polymerzation, Kodansha, Tokyo, 1972, pp. 44-45.
31. H. Uelzmann, J. Polym. Sci. 1958, 32, 457-476; F. Patat, H. J. Sinn, Angew. Chem. 1958, 70, 496-500; G. Natta, I. Pasquon, Adv. Catal. 1959, 11, 1-66; G. Natta, G. Mazzanti, Tetrahedron 1960, 86-100; M. L. Huggins, J. Polym. Sci. 1960, 48, 473-475; G. Natta, I. Pasquon, A. Zambelli, G. Gatti, J. Polym. Sci. 1961, 51, 387-398; F. Danusso, D. Sianesi, Chim. Ind. 1962, 44, 474-482.
32. H. Uelzmann, J. Polym. Sci. 1958, 32, 457-476; F. Patat, H. J. Sinn, Angew. Chem. 1958, 70, 496-500; G. Natta, I. Pasquon, Adv. Catal. 1959, 11, 1-66; G. Natta, G. Mazzanti, Tetrahedron 1960, 86-100; M. L. Huggins, J. Polym. Sci. 1960, 48, 473-475; G. Natta, I. Pasquon, A. Zambelli, G. Gatti, J. Polym. Sci. 1961, 51, 387-398; F. Danusso, D. Sianesi, Chim. Ind. 1962, 44, 474-482.
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42. 2 see P. Corradini, V. Busico, G. Guerra in Transition Metals and Organometallics as Catalysts for Olefin Polymerization (Eds.: W. Kaminsky, H. Sinn), Springer, Berlin, 1988, pp. 337-348; P. Corradini, V. Busico, G. Guerra in Comprehensive Polymer Science, Vol. 4 (Eds.: G. Allen, J. C. Bevington), Pergamon, Oxford, 1989, pp. 29-50; G. Monaco, M. Toto, G. Guerra, P. Corradini, L. Cavallo, Macromolecules 2000, 33, 8953-8962; for the structure of these complexes see also: H. Weiss, M. Boero, M. Parrinello, Macromol. Symp. 2001, 173, 137-147.
43. 2 see P. Corradini, V. Busico, G. Guerra in Transition Metals and Organometallics as Catalysts for Olefin Polymerization (Eds.: W. Kaminsky, H. Sinn), Springer, Berlin, 1988, pp. 337-348; P. Corradini, V. Busico, G. Guerra in Comprehensive Polymer Science, Vol. 4 (Eds.: G. Allen, J. C. Bevington), Pergamon, Oxford, 1989, pp. 29-50; G. Monaco, M. Toto, G. Guerra, P. Corradini, L. Cavallo, Macromolecules 2000, 33, 8953-8962; for the structure of these complexes see also: H. Weiss, M. Boero, M. Parrinello, Macromol. Symp. 2001, 173, 137-147.
44. 2 see P. Corradini, V. Busico, G. Guerra in Transition Metals and Organometallics as Catalysts for Olefin Polymerization (Eds.: W. Kaminsky, H. Sinn), Springer, Berlin, 1988, pp. 337-348; P. Corradini, V. Busico, G. Guerra in Comprehensive Polymer Science, Vol. 4 (Eds.: G. Allen, J. C. Bevington), Pergamon, Oxford, 1989, pp. 29-50; G. Monaco, M. Toto, G. Guerra, P. Corradini, L. Cavallo, Macromolecules 2000, 33, 8953-8962; for the structure of these complexes see also: H. Weiss, M. Boero, M. Parrinello, Macromol. Symp. 2001, 173, 137-147.
45. 2 see P. Corradini, V. Busico, G. Guerra in Transition Metals and Organometallics as Catalysts for Olefin Polymerization (Eds.: W. Kaminsky, H. Sinn), Springer, Berlin, 1988, pp. 337-348; P. Corradini, V. Busico, G. Guerra in Comprehensive Polymer Science, Vol. 4 (Eds.: G. Allen, J. C. Bevington), Pergamon, Oxford, 1989, pp. 29-50; G. Monaco, M. Toto, G. Guerra, P. Corradini, L. Cavallo, Macromolecules 2000, 33, 8953-8962; for the structure of these complexes see also: H. Weiss, M. Boero, M. Parrinello, Macromol. Symp. 2001, 173, 137-147.
46. 2 see P. Corradini, V. Busico, G. Guerra in Transition Metals and Organometallics as Catalysts for Olefin Polymerization (Eds.: W. Kaminsky, H. Sinn), Springer, Berlin, 1988, pp. 337-348; P. Corradini, V. Busico, G. Guerra in Comprehensive Polymer Science, Vol. 4 (Eds.: G. Allen, J. C. Bevington), Pergamon, Oxford, 1989, pp. 29-50; G. Monaco, M. Toto, G. Guerra, P. Corradini, L. Cavallo, Macromolecules 2000, 33, 8953-8962; for the structure of these complexes see also: H. Weiss, M. Boero, M. Parrinello, Macromol. Symp. 2001, 173, 137-147.
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50. -1: S. Dainton, D. M. Evans, F. E. Hoare, T. P. Melia, Polymer 1962, 3, 286-296; B. Wunderlich, J. Chem. Phys. 1962, 37, 1203-1207; T. R. Das, N. R. Kuloor, Indian J. Technol. 1967, 5, 86-91; K. Goldmann in The Physical Properties of Ethylene (Ed.: S. A. Miller), Ernest Benn, London, 1969, pp. 150-168; K. J. Ivin in Polymer Handbook (Eds.: J. Brandrup, E. H. Immergut), Wiley, New York, 1975, p. 11.
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54. With these data given in ref. [23] for a degree of crystallinity of 50% the equilibrium concentrations of ethylene at 80°C can be calculated: F. S. Dainton, K. J. Ivin, Q. Rev. (London) 1958, 12, 61-92.
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58. 5 components. The composition can be determined by analyzing the gaseous components after alcoholysis and hydrolysis. Isoprenylaluminum is a industrial product: H. Hoberg, M. Martin, R. Rienäcker, K. Zosel, K. Ziegler, Brennst.-Chem. 1969, 50, 217-221.
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60. The physico-chemical processes of the catalyst preparation are described in detail: R. P. Nielson in Transition Metal Catalyzed Polymerizations (Eds.: R. P. Quirk, H. L. Hsieh, G. B. Klingensmith, P. J. T. Tait), harwood academic publishers, London, 1983, pp. 47-82.
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65. P. Galli, E. Susa, G. Di Drusco (Montecatini Edison S.p.A.), DE 2000585, 1970 [Chem. Abstr. 1970, 73, 56566]; A. Mayr, E. Susa, G. Di Drusco (Montecatini Edison S.p.A.), DE 2013730, 1970 [Chem. Abstr. 1970, 73, 121062]; P. Galli, L. Luciani, G. Cecchin, Angew. Makromol. Chem. 1981, 94, 63-90; P.C. Barbé, G. Cecchin, L. Noristi, Adv. Polym. Sci. 1986, 81, 1-81; F. Auriemma, G. Talarico, P. Corradini in Progress and Development of Catalytic Olefin Polymerization (Eds.: T. Sano, T. Uozumi, H. Nakatani, M. Terano), Technology and Education Publishers, Tokyo, 2000, pp. 7-15.
66. P. Galli, E. Susa, G. Di Drusco (Montecatini Edison S.p.A.), DE 2000585, 1970 [Chem. Abstr. 1970, 73, 56566]; A. Mayr, E. Susa, G. Di Drusco (Montecatini Edison S.p.A.), DE 2013730, 1970 [Chem. Abstr. 1970, 73, 121062]; P. Galli, L. Luciani, G. Cecchin, Angew. Makromol. Chem. 1981, 94, 63-90; P.C. Barbé, G. Cecchin, L. Noristi, Adv. Polym. Sci. 1986, 81, 1-81; F. Auriemma, G. Talarico, P. Corradini in Progress and Development of Catalytic Olefin Polymerization (Eds.: T. Sano, T. Uozumi, H. Nakatani, M. Terano), Technology and Education Publishers, Tokyo, 2000, pp. 7-15.
67. P. Galli, E. Susa, G. Di Drusco (Montecatini Edison S.p.A.), DE 2000585, 1970 [Chem. Abstr. 1970, 73, 56566]; A. Mayr, E. Susa, G. Di Drusco (Montecatini Edison S.p.A.), DE 2013730, 1970 [Chem. Abstr. 1970, 73, 121062]; P. Galli, L. Luciani, G. Cecchin, Angew. Makromol. Chem. 1981, 94, 63-90; P.C. Barbé, G. Cecchin, L. Noristi, Adv. Polym. Sci. 1986, 81, 1-81; F. Auriemma, G. Talarico, P. Corradini in Progress and Development of Catalytic Olefin Polymerization (Eds.: T. Sano, T. Uozumi, H. Nakatani, M. Terano), Technology and Education Publishers, Tokyo, 2000, pp. 7-15.
68. P. Galli, E. Susa, G. Di Drusco (Montecatini Edison S.p.A.), DE 2000585, 1970 [Chem. Abstr. 1970, 73, 56566]; A. Mayr, E. Susa, G. Di Drusco (Montecatini Edison S.p.A.), DE 2013730, 1970 [Chem. Abstr. 1970, 73, 121062]; P. Galli, L. Luciani, G. Cecchin, Angew. Makromol. Chem. 1981, 94, 63-90; P.C. Barbé, G. Cecchin, L. Noristi, Adv. Polym. Sci. 1986, 81, 1-81; F. Auriemma, G. Talarico, P. Corradini in Progress and Development of Catalytic Olefin Polymerization (Eds.: T. Sano, T. Uozumi, H. Nakatani, M. Terano), Technology and Education Publishers, Tokyo, 2000, pp. 7-15.
69. L. L. Böhm, Macromol. Symp. 2001, 173, 55-63.
70. L. Luciani, N. Kashiwa, P. Barbé, A. Toyota (Montedison, Mitsui Petrochemical), US 4226714, 1975 [Chem. Abstr. 1977, 87, 68693]; N. Kashiwa, Polym. J. 1980, 12, 603-608; N. Kashiwa, J. Yoshitake, T. Tsutsui in Transition Metals and Organometallics as Catalysts for Olefin Polymerization (Ed.: W. Kaminsky, H. J. Sinn), Springer, Berlin, 1988, pp. 33-43.
71. L. Luciani, N. Kashiwa, P. Barbé, A. Toyota (Montedison, Mitsui Petrochemical), US 4226714, 1975 [Chem. Abstr. 1977, 87, 68693]; N. Kashiwa, Polym. J. 1980, 12, 603-608; N. Kashiwa, J. Yoshitake, T. Tsutsui in Transition Metals and Organometallics as Catalysts for Olefin Polymerization (Ed.: W. Kaminsky, H. J. Sinn), Springer, Berlin, 1988, pp. 33-43.
72. L. Luciani, N. Kashiwa, P. Barbé, A. Toyota (Montedison, Mitsui Petrochemical), US 4226714, 1975 [Chem. Abstr. 1977, 87, 68693]; N. Kashiwa, Polym. J. 1980, 12, 603-608; N. Kashiwa, J. Yoshitake, T. Tsutsui in Transition Metals and Organometallics as Catalysts for Olefin Polymerization (Ed.: W. Kaminsky, H. J. Sinn), Springer, Berlin, 1988, pp. 33-43.
73. M. Ferraris, F. Rosati, S. Parodi, E. Giannetti, G. Motroni, E. Albizzati (Montedison S.p.A.), DE 2933997, 1980 [Chem. Abstr. 1980, 92, 199055].
74. G. Thum (Hoechst AG), DE 3620060, 1987 [Chem. Abstr. 1988, 108, 205257]; W. Breuers, R. Lecht, L. Böhm (Hoechst AG), EP 0613909, 1994 [Chem. Abstr. 1995, 122, 134146].
75. G. Thum (Hoechst AG), DE 3620060, 1987 [Chem. Abstr. 1988, 108, 205257]; W. Breuers, R. Lecht, L. Böhm (Hoechst AG), EP 0613909, 1994 [Chem. Abstr. 1995, 122, 134146].
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77. N. J. Turowa, B. A. Popowkin, A. W. Nowoselowa, Z. Anorg. Allg. Chem. 1969, 365, 100-112.
78. G. Lagally in Fließverhalten von Stoffen und Stoff-gemischen (Ed.: W.-M. Kulicke), Hüthig & Wepf, Basel, 1986, pp. 147-186.
79. R. B. Richards, Trans. Faraday Soc. 1946, 42, 10-28; F. Hamada, K. Fujisawa, A. Nakajima, Polym. J. 1973, 4, 316-322; H. Horacek, Makromol. Chem. Suppl. 1975, 1, 415-439; Y. Kodama, F.L. Swinton, Br Polym. J. 1978, 10, 191-200; Y. Kodama, F. L. Swinton, Br. Polym. J. 1978, 10, 201-204.
80. R. B. Richards, Trans. Faraday Soc. 1946, 42, 10-28; F. Hamada, K. Fujisawa, A. Nakajima, Polym. J. 1973, 4, 316-322; H. Horacek, Makromol. Chem. Suppl. 1975, 1, 415-439; Y. Kodama, F.L. Swinton, Br Polym. J. 1978, 10, 191-200; Y. Kodama, F. L. Swinton, Br. Polym. J. 1978, 10, 201-204.
81. R. B. Richards, Trans. Faraday Soc. 1946, 42, 10-28; F. Hamada, K. Fujisawa, A. Nakajima, Polym. J. 1973, 4, 316-322; H. Horacek, Makromol. Chem. Suppl. 1975, 1, 415-439; Y. Kodama, F.L. Swinton, Br Polym. J. 1978, 10, 191-200; Y. Kodama, F. L. Swinton, Br. Polym. J. 1978, 10, 201-204.
82. R. B. Richards, Trans. Faraday Soc. 1946, 42, 10-28; F. Hamada, K. Fujisawa, A. Nakajima, Polym. J. 1973, 4, 316-322; H. Horacek, Makromol. Chem. Suppl. 1975, 1, 415-439; Y. Kodama, F.L. Swinton, Br Polym. J. 1978, 10, 191-200; Y. Kodama, F. L. Swinton, Br. Polym. J. 1978, 10, 201-204.
83. R. B. Richards, Trans. Faraday Soc. 1946, 42, 10-28; F. Hamada, K. Fujisawa, A. Nakajima, Polym. J. 1973, 4, 316-322; H. Horacek, Makromol. Chem. Suppl. 1975, 1, 415-439; Y. Kodama, F.L. Swinton, Br Polym. J. 1978, 10, 191-200; Y. Kodama, F. L. Swinton, Br. Polym. J. 1978, 10, 201-204.
84. L. Mandelkern in Comprehensive Polymer Science, Vol. 2 (Eds.: G. Allen, J. C. Bevington), Pergamon, Oxford, 1989, pp. 363-414 (see also pp. 397-399).
85. This concerns pearl, suspension, emulsion, and Gas-phase polymerization: H. Gerrens in Ullmanns Encyclopädie der technischen Chemie, Vol. 19 (Eds.: E. Bartholomé, E. Bieckert, H. Hellmann, H. Ley, M. Weigert, E. Weise), Verlag Chemie, Weinheim, 1980, pp. 107-165; H. Gerrens, Chem. Ing. Tech. 1982, 52, 477-488.
86. This concerns pearl, suspension, emulsion, and Gas-phase polymerization: H. Gerrens in Ullmanns Encyclopädie der technischen Chemie, Vol. 19 (Eds.: E. Bartholomé, E. Bieckert, H. Hellmann, H. Ley, M. Weigert, E. Weise), Verlag Chemie, Weinheim, 1980, pp. 107-165; H. Gerrens, Chem. Ing. Tech. 1982, 52, 477-488.
87. For the slurry polymerization process the viscosity of the slurry depends only on physical data, such as particle size, particle shape, bulk density, and the volume fraction in petrol. It is not dependent on average molecular mass of polyethylene. Therefore with this process ultrahigh molecular-mass polyethylene can be produced: M. Mooney, J. Colloid Sci. 1951, 6, 162-170; T. B. Lewis, L. E. Nielson, Trans. Soc. Rheol. 1968, 12, 421-443; R. Michael, K. H. Reichert, Chem. Ing. Tech. 1984, 56, 48-50.
88. For the slurry polymerization process the viscosity of the slurry depends only on physical data, such as particle size, particle shape, bulk density, and the volume fraction in petrol. It is not dependent on average molecular mass of polyethylene. Therefore with this process ultrahigh molecular-mass polyethylene can be produced: M. Mooney, J. Colloid Sci. 1951, 6, 162-170; T. B. Lewis, L. E. Nielson, Trans. Soc. Rheol. 1968, 12, 421-443; R. Michael, K. H. Reichert, Chem. Ing. Tech. 1984, 56, 48-50.
89. For the slurry polymerization process the viscosity of the slurry depends only on physical data, such as particle size, particle shape, bulk density, and the volume fraction in petrol. It is not dependent on average molecular mass of polyethylene. Therefore with this process ultrahigh molecular-mass polyethylene can be produced: M. Mooney, J. Colloid Sci. 1951, 6, 162-170; T. B. Lewis, L. E. Nielson, Trans. Soc. Rheol. 1968, 12, 421-443; R. Michael, K. H. Reichert, Chem. Ing. Tech. 1984, 56, 48-50.
90. W. R. Schmeal, J. R. Street, AIChE J. 1971, 17, 1188-1197; E. J. Nagel, V. A. Kiriliov, W. H. Ray, Ind. Eng. Chem. Prod. Res. Dev. 1880, 19, 372-379; T. W. Taylor, K. Y. Choi, H. Yuan, W. H. Ray in Transition Metal Catalyzed Polymerization (Ed.: R. P. Quirk), Harwood, London, 1983, pp. 191-222; R. A. Hutchinson, C. M. Chen, W. H. Ray, J. Appl. Polym. Sci. 1992, 44, 1389-1414.
91. W. R. Schmeal, J. R. Street, AIChE J. 1971, 17, 1188-1197; E. J. Nagel, V. A. Kiriliov, W. H. Ray, Ind. Eng. Chem. Prod. Res. Dev. 1880, 19, 372-379; T. W. Taylor, K. Y. Choi, H. Yuan, W. H. Ray in Transition Metal Catalyzed Polymerization (Ed.: R. P. Quirk), Harwood, London, 1983, pp. 191-222; R. A. Hutchinson, C. M. Chen, W. H. Ray, J. Appl. Polym. Sci. 1992, 44, 1389-1414.
92. W. R. Schmeal, J. R. Street, AIChE J. 1971, 17, 1188-1197; E. J. Nagel, V. A. Kiriliov, W. H. Ray, Ind. Eng. Chem. Prod. Res. Dev. 1880, 19, 372-379; T. W. Taylor, K. Y. Choi, H. Yuan, W. H. Ray in Transition Metal Catalyzed Polymerization (Ed.: R. P. Quirk), Harwood, London, 1983, pp. 191-222; R. A. Hutchinson, C. M. Chen, W. H. Ray, J. Appl. Polym. Sci. 1992, 44, 1389-1414.
93. W. R. Schmeal, J. R. Street, AIChE J. 1971, 17, 1188-1197; E. J. Nagel, V. A. Kiriliov, W. H. Ray, Ind. Eng. Chem. Prod. Res. Dev. 1880, 19, 372-379; T. W. Taylor, K. Y. Choi, H. Yuan, W. H. Ray in Transition Metal Catalyzed Polymerization (Ed.: R. P. Quirk), Harwood, London, 1983, pp. 191-222; R. A. Hutchinson, C. M. Chen, W. H. Ray, J. Appl. Polym. Sci. 1992, 44, 1389-1414.
94. L. Böhm, Chem. Ing. Tech. 1984, 58, 674-684; L. L. Böhm, R. Franke, G. Thum in Transition Metals and Organometallics as Catalysts for Olefin Polymerization (Eds.: W. Kaminsky, H. Sinn), Springer, Berlin, 1988, pp. 391-403; this particle-forming process can also be described with other models, such as the "multigrain model": R. A. Hutchinson, C. M. Chen, W. H. Ray, J. Appl. Polym. Sci. 1992, 44, 1389-1414; the simpliest model is the "polymeric flow model"; it describes the particle-forming process in a simple and clear way, the calculated and experimental data correspond well, therefore it is of importance still today: T. Mc Kenna, V. Mattioli, Macromol. Symp. 2001, 173, 149-162.
95. L. Böhm, Chem. Ing. Tech. 1984, 58, 674-684; L. L. Böhm, R. Franke, G. Thum in Transition Metals and Organometallics as Catalysts for Olefin Polymerization (Eds.: W. Kaminsky, H. Sinn), Springer, Berlin, 1988, pp. 391-403; this particle-forming process can also be described with other models, such as the "multigrain model": R. A. Hutchinson, C. M. Chen, W. H. Ray, J. Appl. Polym. Sci. 1992, 44, 1389-1414; the simpliest model is the "polymeric flow model"; it describes the particle-forming process in a simple and clear way, the calculated and experimental data correspond well, therefore it is of importance still today: T. Mc Kenna, V. Mattioli, Macromol. Symp. 2001, 173, 149-162.
96. L. Böhm, Chem. Ing. Tech. 1984, 58, 674-684; L. L. Böhm, R. Franke, G. Thum in Transition Metals and Organometallics as Catalysts for Olefin Polymerization (Eds.: W. Kaminsky, H. Sinn), Springer, Berlin, 1988, pp. 391-403; this particle-forming process can also be described with other models, such as the "multigrain model": R. A. Hutchinson, C. M. Chen, W. H. Ray, J. Appl. Polym. Sci. 1992, 44, 1389-1414; the simpliest model is the "polymeric flow model"; it describes the particle-forming process in a simple and clear way, the calculated and experimental data correspond well, therefore it is of importance still today: T. Mc Kenna, V. Mattioli, Macromol. Symp. 2001, 173, 149-162.
97. L. Böhm, Chem. Ing. Tech. 1984, 58, 674-684; L. L. Böhm, R. Franke, G. Thum in Transition Metals and Organometallics as Catalysts for Olefin Polymerization (Eds.: W. Kaminsky, H. Sinn), Springer, Berlin, 1988, pp. 391-403; this particle-forming process can also be described with other models, such as the "multigrain model": R. A. Hutchinson, C. M. Chen, W. H. Ray, J. Appl. Polym. Sci. 1992, 44, 1389-1414; the simpliest model is the "polymeric flow model"; it describes the particle-forming process in a simple and clear way, the calculated and experimental data correspond well, therefore it is of importance still today: T. Mc Kenna, V. Mattioli, Macromol. Symp. 2001, 173, 149-162.
98. Thiele has used such equations to describe the synthesis of low-molecular-mass compounds in catalyst particles: E. W. Thiele, Ind. Eng. Chem. 1939, 21, 916-920; in contrast to the polymerization process described in this review, for the catalytic processes described by Thiele, the size and structure of the catalyst particle remains unchanged.
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