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1 Engineering Plastics Produced by Metallocene Catalysts(Walter Kaminsky)1

1.1 Introduction1

1.2 Random Cycloolefin Copolymers2

1.3 Alternating Cyclo Olefin Copolymers4

1.4 Syndiotactic Polystyrene8

1.5 Experimental Part10

1.6 Conclusion10

References10

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 China12

2.1.1 Metallocene catalyst for ethylene polymerization12

2.1.2 Metallocene catalysts for propylene polymerization13

2.1.3 Metallocene catalyst for syndiotactic polystryene14

2.1.4 Others14

2.2 The Prospects of R(D of Metallocene in China)15

References15

3 The Effect of the Molecular Structure on the Properties of Metallocene Catalysts(Helmut G.Alt)16

3.1 Introduction16

3.2 Results and Discussion16

3.2.1 Catalysts with high activities16

3.2.2 Syndiospecific catalysts for propene polymerization19

3.2.3 Heterogenization of catalysts21

3.2.4 New materials25

3.3 Conclusions25

References25

4 Forever Young-47 Years of Ziegler Catalysts(Wolf Jurgen Richter)26

4.1 In the Beginning: al-Chemy26

4.2 The Breakthrough: Zirconium and Titanium Co-Catalysts28

4.3 The Legal Battle32

4.4 New Generations of Ziegler Catalysts33

References33

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 Introduction35

5.2 Results and Discussion36

5.2.1 Ligand and complex synthesis36

5.2.2 Propene polymerizations38

5.3 Mechanisms of Stereoerror Formation41

5.4 Conclusion45

5.5 Experimental Section46

Footnotes49

6 Stereospecific Olefin Polymerization with Homogeneous and Heterogenized Metallocenes(Gerhard Fink)52

6.1 Introduction52

6.2 Results and Discussion52

References57

7 Study on Propylene Polymerization Using Unbridged Metallocene Catalysts(Linxian Feng,Zhiqiang Fan,Yinbang Zhu,Tariq Yasin)59

7.1 Introduction59

7.2 Experimental Part60

7.2.1 Materials60

7.2.2 Catalyst preparation60

7.2.3 Polymerization procedure60

7.2.4 Polymer characterization61

7.3 Results and Discussion61

7.3.1 Polymerization of propylene61

7.3.2 Microstructure analysis63

7.4 Conclusion67

References67

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 Isobutene68

8.2 Anion Effects in Metallocene Propene Polymerization Catalysts72

8.3 Conclusion80

References80

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 Introduction82

9.2 Formation and Characterization of Some Metallocene-Betaine-Catalyst Systems83

9.3 Catalytic Olefin Polymerization and Stoichiometric Alkene Insertion Reactions87

9.4 Some Conclusions91

References91

10 New Carborane-Based Cocatalysts: Synthesis,Structural Characterization and Potential Applications in Olefin Polymerization(Zuowei Xie)94

10.1 Introduction94

10.2 Highly Halogenated Carborane Anions95

10.3 Mixed Halocarborane Anions97

10.4 Highly Alkylated Carborane Anions100

10.5 Weakly Coordinating Nature101

References103

11 Novel Intramolecular Coordination,Elimination and Cyclization of Alkoxybenzyl-Substituted Cyclopentadienyl Titanium and Zirconium Complexes(Yanlong Qian and Jiling Huang)105

References116

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 Introduction117

12.2 Results and Discussion119

12.2.1 Activity119

12.2.2 Effect of catalyst concentration125

12.2.3 Effect of activation time126

12.2.4 Effect of reaction time126

12.2.5 Effect of temperature127

12.2.6 Oligomer analyses128

12.2.7 Oligomer characteristics132

12.2.8 Summary136

12.3 Experimental Section136

References138

13 Ethylene Oligomerization by Cobalt(ll) Diimine Complexes/EAO(Bin Zhou,Mingxing Qian,Mei Wang,Ren He)143

13.1 Introduction143

13.2 Experimental Details144

13.3 Results and Discussion144

13.3.1 The effect of reaction temperature on catalytic activity and product distribution144

13.3.2 The effect of Al/Co ratios on catalytisc activity and product distribution145

13.3.3 The effect of reaction time on catalytic activity and product distribution146

13.4 Conclusions147

References148

14 Water as a Reaction Medium for Coordination Polymerization of Ethylene(Anke Held,Florian M.Bauers and Stefan Mecking)149

14.1 Introduction149

14.2 Results and Discussion150

14.3 Conclusion155

References156

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 Introduction159

15.2 Experiments160

15.2.1 ligands160

15.2.2 Nickel(II) complexes161

15.2.3 X-ray structure162

15.2.4 Ethylene oligomerization163

15.3 Results and Discussion163

15.3.1 Complexes of(N-N)-MAO163

15.3.2 Complexes of(N-P)-MAO163

15.3.3 Complexes of(N-O)-MAO164

References164

16 Preparation of LLDPE Using a Combination Ti(OBu)4-Metallocene Catalytic System(Zhongyang Liu.Demin Xu,Dawei He,Youliang Hu)165

16.1 Introduction165

16.2 Experimental Details165

16.2.1 Materials165

16.2.2 Polymerization166

16.2.3 Polymer analysis166

16.3 Results and Discussion166

16.3.1 Make MAO and metallocene as a complex166

16.3.2 Use of B(C6F5)3/AIEt3 as the co-activator of metallocene169

16.3.3 Use of metallocene supported on the SiO2 as copolymerization catalyst170

16.4 Conclusions171

References172

17 Polymerized Metallocene Catalysts for Ethylene Polymerization(Guangyuan Zhou,Guoxin Jin)173

17.1 Introduction173

17.2 Synthesis of Polymerized Catalysts174

17.3 Ethylene Polymerization Under Normal Pressure178

17.4 Ethylene Polymerization Under High Pressure182

References183

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 Introduction184

18.2 Results and Discussion185

18.2.1 Preparation of dinuclear catalysts 1—6185

18.2.2 1H NMR spectra186

18.2.3 Mass spectra187

18.2.4 Polymerization studies187

18.3 Conclusion191

18.4 Experimental Details191

18.4.1 Preparation of [Me2SiSiMe2(C5H4)2](C5H5ZrCl2)2(2)191

18.4.2 Preparation of 3—6192

18.4.3 Ethylene polymerization192

References192

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 Introduction194

19.2 Experimental195

19.2.1 Catalysts195

19.2.2 Ethylene polymerization195

19.2.3 XPS characterization195

19.3 Results and Discussion195

19.4 Conclusions198

References199

20 Synthesis of Powdery Syndiotactic Polystyrene with Homogeneous Metallocene Catalysts—Kinetics and Morphologies(Bo geng Li,Rong Fan,and Kun Cao)200

20.1 Introduction200

20.2 Experimental Details200

20.2.1 Materials200

20.2.2 Polymerization201

20.2.3 Characterization201

20.3 Results and Discussion201

20.3.1 Kinetics of bulk polymerization201

20.3.2 Morphologies of as-polymerized sPS samples205

20.4 Conclusions206

References206

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 Introduction207

21.2 Experimental Details208

21.2.1 Materials208

21.2.2 Polymerization208

21.2.3 Characterizaion208

21.3 Results and Discussion209

21.3.1 Styrene syndiospecific polymerization209

21.3.2 Butylene-1 polymerization210

21.3.3 Copolymerization of styrene and butene-1212

21.4 Conclusions215

References216

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 Introduction217

22.2 Results and Discussion218

22.2.1 Alkyl cation formation and ethylene polymerization218

22.2.2 Rare earth catalysts220

22.3 Conclusion224

References224

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 Lanthanidoccnes226

23.2 Preparation of Liquid Crystalline Polymethacrylates Using Samarocenes as Catalysts228

References231

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 Introduction233

24.2 Synthesis and Structural Characterization of C1,Cs and C2 Symmetric ansa-Lanthanocenes Complexes234

24.2.1 Synthesis of one-atom bridged fluorenyl cyclopentadienyl ansa-lanthanocenes complexes with C1 or Cs symmetry234

24.2.2 Synthesis of racemic ether bridged bis(indenyl) lanthanocene complexes with C2-symmetry237

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-symmetry238

24.3.2 Catalytic activity of racemic ether bridged bis(indenyl) lanthanocene amides and hydrolcarbyls with C2-symmetry239

24.4 Conclusion240

References241

25 Polymerization Behaviors of Tin-Bridged Neodynocene and Yttrocene Catalysts(Junquan Sun,Zhida Pan,Weiqiu Hu,and Chengfeng Liang)243

25.1 Introduction243

25.2 Experimental244

25.2.1 Materials244

25.2.2 Polymerization244

25.2.3 Measurement245

25.3 Results and Discussion245

25.3.1 Polymerization of ethylene245

25.3.2 Polymerization of methyl methacrylate247

25.3.3 Polymerization of ε-caprolactone251

References253