Catalytic Synthesis of Alkene-Carbon Monoxide Copolymers and Cooligomers

217 2. COPOLYMERIZATION OF PROPENE OR HIGHER I-ALKENES WITH 218 CARBON MONOXIDE 2. 1. Ligands and polymerization conditions 218 2. 2. Spiroketal formation 221 2. 3. Enantioselectivity 222 2. 4. Higher I-Alkenes 226 3. COPOLYMERIZATION OF STYRENE OR ITS DERIVATIVES WITH 226 CARBON MONOXIDE 4. COPOLYMERIZATION OF OTHER OLEANS WITH CARBON MONOXIDE 230 5. ASYMMETRIC TERPOLYMERIZATION OF MORE THAN Two KINDS OF 232 OLEFINS WITH CARBON MONOXIDE 6. POLYKETONE CONFORMATION 233 7. CONCLUSION 234 Chapter 8. Chain Propagation Mechanisms 237 Ayusman Sen 1. INTRODUCTION 237 2. PALLADIUM (II) BASED SYSTEMS 238 3. NICKEL (II) BASED SYSTEMS 256 4. RHODIUM (I) BASED SYSTEMS 257 5. CONCLUSION 261 Chapter 9. Theoretical Studies on Copolymerization of Polar Monomers 265 Peter Margl, Artur Michalak, and Tom Ziegler 1. INTRODUCTION 265 2. COPOLYMERIZATION OF CARBON MONOXIDE WITH ETHYLENE 267 2. 1. Experimental and calculated rates for the insertion processes for 267 copolymerization catalysed by Pd(II) systems. 2. 2. A more detailed look at the productive and unproductive cycles 270 in copolymerization catalysed by Pd(II) complexes. 2. 2. 1. The productive cycle 270 2. 2. 2. C2H4 misinsertion into an ethylene terminated polyketone 275 chain 2. 3. Experimental and calculated rates for the insertion processes for 277 alternating copolymerization catalyzed by Ni(II) systems 3. COPOLYMERIZATION OF OLEFINS WITH POLAR MONOMERS OTHER 280 THAN CO 3. 1. Preferred binding mode of oxygen containing monomers 282 3. 2. Preferred binding mode of nitrogen containing monomers 285 3. 3.

Klappentext

The discovery of facile catalytic alternating alkene/carbon monoxide copolymerization has significantly impacted the areas of polymer science, organometallic chemistry, and catalysis. Highly active systems that allow the directed synthesis of compounds ranging from low molecular weight esters, ketones and aldehydes to high molecular weight copolymers are now available. In addition, copolymerizations with high regio, stereo and enantioselectivity have been achieved. Catalytic Synthesis of Alkene-Carbon Monoxide Copolymers and Cooligomers is written by the foremost researchers in the field and provides the first comprehensive coverage of all aspects of the subject. The book draws on journal and patent literature available up to the middle of 2002, as well as hitherto unpublished results. This book is of interest to academic and industrial chemists involved with transition metal catalysis, organometallic chemistry, petrochemicals, and polymeric materials.

Inhalt

1. Introduction and Future Directions.- 1. INTRODUCTION.- 2. FUTURE DIRECTIONS.- 2. Palladium-Catalysed Synthesis of Mono-esters, -ketones, and aldehydes/alcohols.- 1. INTRODUCTION.- 2. METHOXYCARBONYLATION.- 3. PRECISE CONTROL OF THE OXO-SYNTHESIS.- 3. Production of Cooligomers from Carbon Monoxide and Ethene.- I. INTRODUCTION.- 2. OLIGOKETONE SYNTHESIS.- 3. BlDENTATE LIGANDS.- 4. TERMINATION MECHANISMS.- 5. CONTROLLING CHAIN GROWTH THROUGH THE USE OF ALTERNATIVE METALS.- 6. SELECTIVE FORMATION OF 3-PENTANONE.- 7. CONCLUSIONS.- 4. Catalytic Synthesis of Copolymers and Terpolymers.- 1. INTRODUCTION.- 2. PHYSICAL PROPERTIES OF ALIPHATIC POLYKETONES.- 3. COPOLYMERIZATION.- 4. PROCESS DEVELOPMENT.- 5. DETAILED INvESTIGATION OF LIGAND EFFECTS.- 6. THE PHYSICAL STATE OF THE CATALYST.- 7. INITIAL CATALYST PERFORMANCE.- 8. ON THE POSSIBLE ROLE OF OXIDANT PROMOTORS.- 9. SUMMARY AND OUTLOOK.- 5. Chain Transfer Mechanisms.- 1. INTRODUCTION.- 2. POLYMERIZATIONS.- 3. OLIGOMERIZATIONS.- 4. FORMATION OF ESTERS AND ACIDS.- 6. Stereochemical Aspects of Cooligomerization and Copolymerization.- 1. INTRODUCTION.- 2. AROMATIC OLEFINS (STYRENE).- 3. ALIPHATIC OLEFINS (PROPENE).- 4. CYCLOPOLYMERIZATION.- 5. FINAL REMARKS.- 7. Synthesis ofChiral, Optically Active Copolymers.- 1. INTRODUCTION.- 2. COPOLYMERIZATION OF PROPENE OR HIGHER I-ALKENES WITH CARBON MONOXIDE.- 3. COPOLYMERIZATION OF STYRENE OR ITS DERIVATIVES CARBON MONOXIDE.- 4. COPOLYMERIZATION OF OTHER OLEANS WITH CARBON MONOXIDE.- 5. ASYMMETRIC TERPOLYMERIZATION OF MORE THAN TWO KINDS OF OLEFINS WITH CARBON MONOXIDE.- 6. POLYKETONE CONFORMATION.- 7. CONCLUSION.- 8. Chain Propagation Mechanisms.- 1. INTRODUCTION.- 2. PALLADIUM (II) BASED SYSTEMS.- 3. NICKEL (II) BASED SYSTEMS.- 4. RHODIUM (I) BASED SYSTEMS.- 5. CONCLUSION.- 9. Theoretical Studies on Copolymerization of Polar Monomers.- 1. INTRODUCTION.- 2. COPOLYMERIZATION OF CARBON MONOXIDE WITH ETHYLENE.- 3. COPOLYMERIZATION OF OLEFINS WITH POLAR MONOMERS OTHER THAN CO.- 4. CONCLUDING REMARKS.