中德金属有机催化剂和烯烃聚合进展PDF电子书下载

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