Organometallic Reactions and Polymerization

307 Pages·2014·11.654 MB·English

by  Kohtaro Osakada (eds.)

Lecture Notes in Chemistry 85
Kohtaro Osakada Editor
Organometallic
Reactions and
Polymerization
Lecture Notes in Chemistry
Volume 85
Series editors
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Kohtaro Osakada
Editor
Organometallic Reactions
and Polymerization
123
Editor
Kohtaro Osakada
Chemical Resources Laboratory
TokyoInstituteof Technology
Yokohama
Japan
ISSN 0342-4901 ISSN 2192-6603 (electronic)
ISBN 978-3-662-43538-0 ISBN 978-3-662-43539-7 (eBook)
DOI 10.1007/978-3-662-43539-7
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Preface
Olefinpolymerizationusingtransition-metalcatalystshasrevolutionizedmaterials
science and petroleum industry, and created an affluent society worldwide. Thus,
the discovery of ethylene polymerization under low pressure using Ziegler-Natta
catalysts should be ranked among the most important discoveries of the past
century. Research on a homogeneous version of olefin polymerization catalysts,
represented by metallocene catalysts, took off in the 1980s, which resulted in
additional progress in polymer science and technology as well as in related
research fields. The catalysts composed of transition metal complexes have
enabled controlled synthesis of a number of polyolefins and olefin copolymers
with the proper choice of an auxiliary ligand for the molecular transition-metal
complex.Thestructuresoftheabove-mentionedmolecularcatalystscanbeeasily
modified, which improves the reactivity and selectivity of olefin polymerization.
Anotherimportantachievementintheuseofmoleculartransitionmetalcomplexes
ascatalysts istheelucidationofthereaction mechanism ofolefin polymerization.
The exact reaction pathways and detailed account of the stereocontrol of such
polymerization can be discussed on the basis of the catalyst structure and poly-
merization results. Organotransition-metal chemistry has developed together with
coordination polymerization because its fundamental reactions, including the
migratory insertion and b-hydrogen elimination of olefins, play key roles in
polymerization catalyzed by transition-metal complexes. Progress in research on
coordination polymerization continues to generate new polymer materials from
olefins that are economically and environmentally favorable.
This issue of Lecture Note Series contains eight articles covering the poly-
merization using various organotransition-metal catalysts, including early- and
late-transition-metalcomplexes,newtrendsinolefinoligomerization,andrelated
reactions.Alltheauthorshaveensuredthattheirarticleincludesthehistoricaland
scientific backgrounds ofthe field, current researchprogress, andfurther scope of
research. The whole book is designed to deliver eight independent lectures from
the authors. Since the authors involved are well versed in organometallic chem-
istry, the discussion in each chapter is based on a profound understanding of the
reactionsandstructuresoforganotransition-metalcomplexes.Afewtopicsoverlap
among the chapters so that the readers may choose to start reading particular
chaptersinthebookfirst.Weincludedtwofinalchaptersonolefinmetathesisand
cross-coupling polymerization. These two reactions are composed offundamental
v
vi Preface
reactions of organotransition-metal complexes, similar to the coordination poly-
merization, and at present have become crucial materials science and device
technology.
Theprojectofpublishingthisbookinitspresentformstartedwithaninvitation
fromSpringerPublishingtocontributetotheseries‘‘LectureNotesinChemistry’’.
We would like to acknowledge the initiative of Dr. Tien-Yau Luh, editor of the
series of books, and the kind cooperation of Elizabeth Hawkins in bringing this
book to fruition.
Kohtaro Osakada
Contents
1 Olefin Polymerization with Metallocene Catalysts. . . . . . . . . . . . . 1
Takeshi Shiono
1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Elementary Processes of Olefin Polymerization. . . . . . . . . . . . . 3
1.2.1 Initiation and Propagation Reactions. . . . . . . . . . . . . . . 3
1.2.2 Chain Transfer and Termination Reaction . . . . . . . . . . . 3
1.2.3 Molecular Weight and Molecular Weight Distribution. . . 5
1.3 Structure of Vinyl Polymer and Stereospecific
Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.3.1 Stereoregularity of Vinyl Polymer. . . . . . . . . . . . . . . . . 8
1.3.2 Regiochemistry in Propylene Polymerization . . . . . . . . . 8
1.3.3 Origin of Stereospecificity. . . . . . . . . . . . . . . . . . . . . . 10
1.3.4 Polymerization Mechanism and Microtacticity . . . . . . . . 11
1.4 Copolymer and Copolymerization . . . . . . . . . . . . . . . . . . . . . . 16
1.4.1 Structure of Copolymers . . . . . . . . . . . . . . . . . . . . . . . 16
1.4.2 Copolymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
1.5 Characteristics of Metallocene Catalysts. . . . . . . . . . . . . . . . . . 27
1.5.1 Activation Process of Metallocene . . . . . . . . . . . . . . . . 27
1.5.2 Tacticity Control of Polypropylene . . . . . . . . . . . . . . . . 31
1.5.3 Control of Chain Transfer Reaction. . . . . . . . . . . . . . . . 39
1.5.4 Copolymerization of Olefins. . . . . . . . . . . . . . . . . . . . . 41
1.6 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
2 Olefin Polymerization with Half-Metallocene Catalysts . . . . . . . . . 51
Kotohiro Nomura and Jingyu Liu
2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
2.2 Modified Half-Titanocenes as Olefin Polymerization
Catalysts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
2.2.1 Olefin Polymerization by Half-Titanocenes
Containing Aryloxo Ligands. . . . . . . . . . . . . . . . . . . . . 54
2.2.2 Selected Examples in Olefin Polymerization
by Half-Titanocenes Containing the Other Anionic
Ancillary Donor Ligands . . . . . . . . . . . . . . . . . . . . . . . 56
vii
viii Contents
2.2.3 Copolymerizations of Ethylene with Sterically
Encumbered a-olefins . . . . . . . . . . . . . . . . . . . . . . . . . 59
2.2.4 Copolymerization with Cyclic Olefins. . . . . . . . . . . . . . 67
2.3 Syndiospecific Styrene Polymerization and Ethylene/Styrene
Copolymerization Using Half-Titanocenes: Ligand Effects
and Some New Mechanistic Aspects . . . . . . . . . . . . . . . . . . . . 70
2.3.1 Syndiospecific Styrene Polymerization Using
Cp’TiX (Y)–MAO Catalyst Systems. . . . . . . . . . . . . . . 71
2
2.3.2 Ethylene/Styrene Copolymerization Using
Half-Titanocenes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
2.3.3 Role of Anionic Donor Ligand in Ethylene/Styrene
Copolymerization and Syndiospecific Styrene
Polymerization: Mechanistic Considerations. . . . . . . . . . 79
2.4 Summary and Outlook. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
3 Olefin Polymerization with Non-metallocene Catalysts
(Early Transition Metals). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
Kotohiro Nomura and Wenjuan Zhang
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
3.2 Design, Synthesis of Molecular Catalyst with Early
Transition Metals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
3.2.1 Titanium, Zirconium, and Hafnium Complexes. . . . . . . . 90
3.2.2 Vanadium Complexes . . . . . . . . . . . . . . . . . . . . . . . . . 98
3.2.3 Miscellaneous Early Transition Metal
Complex Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
3.3 Summary and Outlook. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
4 Olefin Polymerization with Non-metallocene Catalysts
(Late Transition Metals). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
Daisuke Takeuchi
4.1 Introduction: Brief History of Late Transition Metal Catalysts
for Olefin Polymerization. . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
4.2 Polymerization of Olefins Catalyzed by Cationic Pd
and Ni Complexes with Neutral Ligands . . . . . . . . . . . . . . . . . 121
4.2.1 Cationic Ni and Pd Catalysts with Diimine Ligands . . . . 122
4.2.2 Cationic Complexes with Other Bidentate
Neutral Ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
4.2.3 Cationic Complexes with Monodentate
and Tridentate Ligands . . . . . . . . . . . . . . . . . . . . . . . . 133
4.3 Polymerization of Olefins by Neutral Pd and Ni Complexes
with Monoanionic Ligands. . . . . . . . . . . . . . . . . . . . . . . . . . . 134
Contents ix
4.3.1 Neutral Complexes with Monoanionic N-O Ligands . . . . 134
4.3.2 Phosphinesulfonate Complexes of Pd . . . . . . . . . . . . . . 138
4.3.3 Neutral Complexes with Other Monoanionic Ligands . . . 140
4.4 Polymerization of Olefins by Fe and Co Complexes . . . . . . . . . 141
4.5 Polymerization of Olefins by Other Late Transition
Metal Catalysts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
4.6 Multimetallic Catalysts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
4.7 Olefin Polymerization in Aqueous Media. . . . . . . . . . . . . . . . . 149
4.8 Cyclopolymerization of Non-conjugated Dienes . . . . . . . . . . . . 150
4.9 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
5 Oligomerization of Olefins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
Daisuke Takeuchi and Kohtaro Osakada
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
5.2 Oligomerization of Ethylene. . . . . . . . . . . . . . . . . . . . . . . . . . 170
5.2.1 General Aspect. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
5.2.2 Ethylene Oligomerization to Olefins with Schulz–Flory
Distribution and Dimerization. . . . . . . . . . . . . . . . . . . . 171
5.2.3 Ethylene Oligomerization to a-Olefins
with Poisson Distribution. . . . . . . . . . . . . . . . . . . . . . . 176
5.3 Selective Trimerization of Ethylene. . . . . . . . . . . . . . . . . . . . . 177
5.3.1 Chromium Catalyst. . . . . . . . . . . . . . . . . . . . . . . . . . . 177
5.3.2 Titanium Catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
5.3.3 Tantalum Catalyst. . . . . . . . . . . . . . . . . . . . . . . . . . . . 192
5.3.4 Ruthenium Catalyst. . . . . . . . . . . . . . . . . . . . . . . . . . . 193
5.4 Tetramerization of Ethylene . . . . . . . . . . . . . . . . . . . . . . . . . . 194
5.4.1 Effect of Ligand Structure . . . . . . . . . . . . . . . . . . . . . . 195
5.4.2 Effect of Cocatalysts and Additives. . . . . . . . . . . . . . . . 199
5.4.3 Mechanism of Cr-Catalyzed Ethylene Tetramerization. . . 200
5.5 Dimerization of a-Olefins. . . . . . . . . . . . . . . . . . . . . . . . . . . . 201
5.6 Trimerization of a-Olefins . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
5.7 Cooligomerization of Ethylene and a-Olefins . . . . . . . . . . . . . . 205
5.8 Cooligomerization of Other Vinyl Monomers. . . . . . . . . . . . . . 206
5.9 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
6 Polymerization of Polar Monomers. . . . . . . . . . . . . . . . . . . . . . . . 217
Kyoko Nozaki
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
6.2 Coordination-Addition Polymerization of Polar Monomers. . . . . 218
6.3 Block Copolymerization of Polar Monomers
and Non-polar Monomers. . . . . . . . . . . . . . . . . . . . . . . . . . . . 221