1 Engineering Plastics Produced by Metallocene Catalysts(Walter Kaminsky) 1
1.1 Introduction 1
1.2 Random Cycloolefin Copolymers 2
1.3 Alternating Cyclo Olefin Copolymers 4
1.4 Syndiotactic Polystyrene 8
1.5 Experimental Part 10
1.6 Conclusion 10
References 10
2 Progress and Prospects in Development and Application of Metallocene Catalyst for Polyolefins in China(Dingyi Hong) 12
2.1 Advances in Research on Metallocene Catalyst in China 12
2.1.1 Metallocene catalyst for ethylene polymerization 12
2.1.2 Metallocene catalysts for propylene polymerization 13
2.1.3 Metallocene catalyst for syndiotactic polystryene 14
2.1.4 Others 14
2.2 The Prospects of R(D of Metallocene in China) 15
References 15
3 The Effect of the Molecular Structure on the Properties of Metallocene Catalysts(Helmut G.Alt) 16
3.1 Introduction 16
3.2 Results and Discussion 16
3.2.1 Catalysts with high activities 16
3.2.2 Syndiospecific catalysts for propene polymerization 19
3.2.3 Heterogenization of catalysts 21
3.2.4 New materials 25
3.3 Conclusions 25
References 25
4 Forever Young-47 Years of Ziegler Catalysts(Wolf Jurgen Richter) 26
4.1 In the Beginning: al-Chemy 26
4.2 The Breakthrough: Zirconium and Titanium Co-Catalysts 28
4.3 The Legal Battle 32
4.4 New Generations of Ziegler Catalysts 33
References 33
5 The Role of Stereoerror Formation and Its Relevance for the Design of Tailormade Polypropenes-a Comparison of Different Metallocenes(Jurgen Kukral,Petri Lehmus and Bernhard Rieger) 35
5.1 Introduction 35
5.2 Results and Discussion 36
5.2.1 Ligand and complex synthesis 36
5.2.2 Propene polymerizations 38
5.3 Mechanisms of Stereoerror Formation 41
5.4 Conclusion 45
5.5 Experimental Section 46
Footnotes 49
6 Stereospecific Olefin Polymerization with Homogeneous and Heterogenized Metallocenes(Gerhard Fink) 52
6.1 Introduction 52
6.2 Results and Discussion 52
References 57
7 Study on Propylene Polymerization Using Unbridged Metallocene Catalysts(Linxian Feng,Zhiqiang Fan,Yinbang Zhu,Tariq Yasin) 59
7.1 Introduction 59
7.2 Experimental Part 60
7.2.1 Materials 60
7.2.2 Catalyst preparation 60
7.2.3 Polymerization procedure 60
7.2.4 Polymer characterization 61
7.3 Results and Discussion 61
7.3.1 Polymerization of propylene 61
7.3.2 Microstructure analysis 63
7.4 Conclusion 67
References 67
8 Cationic Metallocenes and Their Versatile Role in Olefin Polymerization Catalysis(Andrew G.Carr,Shaun Garratt,Simon J.Lancaster,Dennis A.Walker,Stefan Beck,Jiamin Zhou,and Manfred Bochmann) 68
8.1 Electrophilic Metallocenes in Non-Ziegler Polymerizations: The Polymerization of Isobutene 68
8.2 Anion Effects in Metallocene Propene Polymerization Catalysts 72
8.3 Conclusion 80
References 80
9 The Development of Single Component Metallocene Betaine Ziegler-Natta Catalysts and Related Systems(Bodo Temme,Jorn Karl,Marc Dahlmann,Klaus Bergander,Gerald Kehr,Heinrich Luftmann,Roland Frohlich,Tim Jodicke,and Gerhard Erker) 82
9.1 Introduction 82
9.2 Formation and Characterization of Some Metallocene-Betaine-Catalyst Systems 83
9.3 Catalytic Olefin Polymerization and Stoichiometric Alkene Insertion Reactions 87
9.4 Some Conclusions 91
References 91
10 New Carborane-Based Cocatalysts: Synthesis,Structural Characterization and Potential Applications in Olefin Polymerization(Zuowei Xie) 94
10.1 Introduction 94
10.2 Highly Halogenated Carborane Anions 95
10.3 Mixed Halocarborane Anions 97
10.4 Highly Alkylated Carborane Anions 100
10.5 Weakly Coordinating Nature 101
References 103
11 Novel Intramolecular Coordination,Elimination and Cyclization of Alkoxybenzyl-Substituted Cyclopentadienyl Titanium and Zirconium Complexes(Yanlong Qian and Jiling Huang) 105
References 116
12 Propene and 1-Hexene Oligomerization with Unbridged Alkyl-substituted Cyclopentadienyl-and Phospholyl-Zirconium/MAO Catalysts-Mechanistic Implications from Oligomer Analyses by NMR,SEC,and MALDI-TOF MS(Christoph Janiak,Katharina C.H.Lang) 117
12.1 Introduction 117
12.2 Results and Discussion 119
12.2.1 Activity 119
12.2.2 Effect of catalyst concentration 125
12.2.3 Effect of activation time 126
12.2.4 Effect of reaction time 126
12.2.5 Effect of temperature 127
12.2.6 Oligomer analyses 128
12.2.7 Oligomer characteristics 132
12.2.8 Summary 136
12.3 Experimental Section 136
References 138
13 Ethylene Oligomerization by Cobalt(ll) Diimine Complexes/EAO(Bin Zhou,Mingxing Qian,Mei Wang,Ren He) 143
13.1 Introduction 143
13.2 Experimental Details 144
13.3 Results and Discussion 144
13.3.1 The effect of reaction temperature on catalytic activity and product distribution 144
13.3.2 The effect of Al/Co ratios on catalytisc activity and product distribution 145
13.3.3 The effect of reaction time on catalytic activity and product distribution 146
13.4 Conclusions 147
References 148
14 Water as a Reaction Medium for Coordination Polymerization of Ethylene(Anke Held,Florian M.Bauers and Stefan Mecking) 149
14.1 Introduction 149
14.2 Results and Discussion 150
14.3 Conclusion 155
References 156
15 Ethylene Oligomerization Promoted by Nickel Complexes with 8-Substituent Quinoline Derivatives(Wenhua Sun,Zilong Li,Changxing Shao,Youliang Hu and Xiuhua Li) 159
15.1 Introduction 159
15.2 Experiments 160
15.2.1 ligands 160
15.2.2 Nickel(II) complexes 161
15.2.3 X-ray structure 162
15.2.4 Ethylene oligomerization 163
15.3 Results and Discussion 163
15.3.1 Complexes of(N-N)-MAO 163
15.3.2 Complexes of(N-P)-MAO 163
15.3.3 Complexes of(N-O)-MAO 164
References 164
16 Preparation of LLDPE Using a Combination Ti(OBu)4-Metallocene Catalytic System(Zhongyang Liu.Demin Xu,Dawei He,Youliang Hu) 165
16.1 Introduction 165
16.2 Experimental Details 165
16.2.1 Materials 165
16.2.2 Polymerization 166
16.2.3 Polymer analysis 166
16.3 Results and Discussion 166
16.3.1 Make MAO and metallocene as a complex 166
16.3.2 Use of B(C6F5)3/AIEt3 as the co-activator of metallocene 169
16.3.3 Use of metallocene supported on the SiO2 as copolymerization catalyst 170
16.4 Conclusions 171
References 172
17 Polymerized Metallocene Catalysts for Ethylene Polymerization(Guangyuan Zhou,Guoxin Jin) 173
17.1 Introduction 173
17.2 Synthesis of Polymerized Catalysts 174
17.3 Ethylene Polymerization Under Normal Pressure 178
17.4 Ethylene Polymerization Under High Pressure 182
References 183
18 Synthesis of Dinuclear Metallocene Complexes and Catalytic Properties for Ethylene Polymerization(Baiquan Wang,Gonglu Tian,Shansheng Xu,Xiuzhong Zhou,Bo Liang and Liang Zhao) 184
18.1 Introduction 184
18.2 Results and Discussion 185
18.2.1 Preparation of dinuclear catalysts 1—6 185
18.2.2 1H NMR spectra 186
18.2.3 Mass spectra 187
18.2.4 Polymerization studies 187
18.3 Conclusion 191
18.4 Experimental Details 191
18.4.1 Preparation of [Me2SiSiMe2(C5H4)2](C5H5ZrCl2)2(2) 191
18.4.2 Preparation of 3—6 192
18.4.3 Ethylene polymerization 192
References 192
19 Plausible Structure of Active Chromium Species on the Phillips Catalyst in the Presence of Cocatalyst(Boping Liu,Pavel Sindelar,Minoru Terano) 194
19.1 Introduction 194
19.2 Experimental 195
19.2.1 Catalysts 195
19.2.2 Ethylene polymerization 195
19.2.3 XPS characterization 195
19.3 Results and Discussion 195
19.4 Conclusions 198
References 199
20 Synthesis of Powdery Syndiotactic Polystyrene with Homogeneous Metallocene Catalysts—Kinetics and Morphologies(Bo geng Li,Rong Fan,and Kun Cao) 200
20.1 Introduction 200
20.2 Experimental Details 200
20.2.1 Materials 200
20.2.2 Polymerization 201
20.2.3 Characterization 201
20.3 Results and Discussion 201
20.3.1 Kinetics of bulk polymerization 201
20.3.2 Morphologies of as-polymerized sPS samples 205
20.4 Conclusions 206
References 206
21 Stereospecific Homo-and Block-Copolymerization of Styrene and Butene-1 with Monotitanocene Catalyst(Fangming Zhu,Qigu Huang,Qing Wu,Shangan Lin) 207
21.1 Introduction 207
21.2 Experimental Details 208
21.2.1 Materials 208
21.2.2 Polymerization 208
21.2.3 Characterizaion 208
21.3 Results and Discussion 209
21.3.1 Styrene syndiospecific polymerization 209
21.3.2 Butylene-1 polymerization 210
21.3.3 Copolymerization of styrene and butene-1 212
21.4 Conclusions 215
References 216
22 Polymerization Catalysts Based on Neutral and Cationic 12-Electron Alkyl and Hydrido Complexes(Jun Okuda,Stefan Arndt,Klaus Beckerle,Kai C.Hultzsch,Piet-Jan Sinnema,Peter Voth,and Thomas P.Spaniol) 217
22.1 Introduction 217
22.2 Results and Discussion 218
22.2.1 Alkyl cation formation and ethylene polymerization 218
22.2.2 Rare earth catalysts 220
22.3 Conclusion 224
References 224
23 New Metallocene Complexes of the Alkaline Earth and the Lanthanide Metals and Their Use as Polymerization Catalysts(Herbert Schumann,Mario Glanz,Jochen Gottfriedsen,Sebastian Dechert) 226
23.1 Synthesis of Carbene Adducts of Group II Metallocenes and Lanthanidoccnes 226
23.2 Preparation of Liquid Crystalline Polymethacrylates Using Samarocenes as Catalysts 228
References 231
24 Synthesis and Structural Characterization of ansa-Lanthanocene Halide,Amide and Hydrocarbyl Complexes with C1,Cs or C2 Symmetry Designed for Stereospecific Polymerization of Methyl Methacrylate(Wanli Nie,Gang Zou,Yaofeng Chen,Jie Sun and) 233
24.1 Introduction 233
24.2 Synthesis and Structural Characterization of C1,Cs and C2 Symmetric ansa-Lanthanocenes Complexes 234
24.2.1 Synthesis of one-atom bridged fluorenyl cyclopentadienyl ansa-lanthanocenes complexes with C1 or Cs symmetry 234
24.2.2 Synthesis of racemic ether bridged bis(indenyl) lanthanocene complexes with C2-symmetry 237
24.3 Polymerization Activity of Methyl Methacrylate(MMA) 238
24.3.1 Catalytic activity of dimethylsilyl-bridged fluorenyl cyclopentadienyl ansa-lanthanocene amides and hydralcarbyls with Cs-symmetry 238
24.3.2 Catalytic activity of racemic ether bridged bis(indenyl) lanthanocene amides and hydrolcarbyls with C2-symmetry 239
24.4 Conclusion 240
References 241
25 Polymerization Behaviors of Tin-Bridged Neodynocene and Yttrocene Catalysts(Junquan Sun,Zhida Pan,Weiqiu Hu,and Chengfeng Liang) 243
25.1 Introduction 243
25.2 Experimental 244
25.2.1 Materials 244
25.2.2 Polymerization 244
25.2.3 Measurement 245
25.3 Results and Discussion 245
25.3.1 Polymerization of ethylene 245
25.3.2 Polymerization of methyl methacrylate 247
25.3.3 Polymerization of ε-caprolactone 251
References 253