Table of Contents

I Kinetics of Olefin Polymerization with Heterogeneous Ziegler-Natta Catalysts.- I-1 Polymerization Kinetics: General Description.- I-2 Phenomenological Kinetic Scheme of Olefin Polymerization.- I-2-a Stationary Polymerization Process.- I-2-b Initial Acceleration Stage of the Polymerization Process.- I-2-c General Scheme of Olefin Polymerization.- I-3 Molecular Weight Growth in the Beginning of a Polymerization Reaction and the Estimation of the Propagation Rate Constants.- I-3-a General Description.- I-3-b Important Particular Cases.- I-3-c Mean Lifetime of a Polymer Chain.- I-3-d Olefin Block-Copolymers.- I-4 Estimation of Propagation Rate Constants from the Kinetics of Consecutive and Statistical Olefin Copolymerization.- I-4-a Consecutive Copolymerization.- I-4-b Statistical Copolymerization.- I-5 Principal Kinetic Parameters for Olefin Homopolymerization and Copolymerization.- I-5-a Propagation Rate Constants of Olefin Polymerization: Comparison with Other Polymerization Reactions.- I-5-b Monomer Reactivity in Isospecific Polymerization and Its Correlation with Olefin Structural Features.- II Heterogeneous Ziegler-Natta Catalysts: Chemistry and Kinetics of the Formation and Functioning of Active Centers.- II-1 Structure of Solid Components of Ziegler-Natta Catalysts.- II-1-a Crystal Structure.- II-1-b Catalyst Grinding.- II-1-c Structure of Supported Ziegler-NauuCatalysts.- II-2 Formation of Active Center of Heterogeneous Ziegler-Natta Catalysts.- II-2-a Interaction between Catalysts and Co-catalysts in the Gas Phase.- II-2-b Interaction between Catalysts and Co-catalysts in Hydrocarbon Suspension.- II-3 Attempts to Study Active Centers Directly.- II-4 Organometallic Compounds and Catalyst Activity.- II-4-a Organometallic Compounds and Center Formation.- II-4-b Destruction of Active Centers by Organometallic Compounds.- II-4-c Organometallic Compounds as Impurity Scavengers.- II-4-d Organometallic Compounds and the Number and Activity of Polymerization Centers.- II-4-e Polymerization with Various Organometallic Compounds and Their Mixtures.- II-5 Effects of Catalyst Poisons and Modifiers. The Measurement of Active Center Concentration 153.- II-5-a Water 154.- II-5-b Alcohols 159.- II-5-c Measurement of Active Center Concentration Based on Alcohol Reactions.- II-5-d Inorganic Poisons Interacting with Organometallic Compounds.- II-5-e Organic Esters, Ketones, and Ethers.- II-5-f Amines.- II-5-g Modification of TiCl3-AlEtCl2 Systems.- II-5-h Poisons Mainly Affecting Active Centers.- II-6 Concentration of Active Centers and Their Location in the Heterogeneous Catalysts.- II-6-a Concentration of Active Centers.- II-6-b Location of Active Centers on the Catalyst Surface.- II-6-c Activity of Different Modifications of TiCl3.- II-7 Origins of Catalyst Instability.- II-8 Monomer Coordination Stage: Its Chemical and Kinetic Manifestations.- III Stereospecificity of Heterogeneous Ziegler-Natta Catalysts.- III-1 Chemistry of Olefin Polymerization.- III-1-a Normal Reaction Pattern.- III-1-b Monomer Unit Inversion.- III-1-c Monomer Isomerization.- III-2 Methods of Measurement of polyolefin Stereoregularity.- III-2-a Nuclear Magnetic Resonance. Sequence Classification.- III-2-b Infrared Spectroscopy.- III-2-c Melting Point and Polyolefin Stereoregularity.- III-3 Enantiomorphous Statistical Model of Stereospecific Olefin and its Experimental Polymerization Proof.- III-4 Statistics of Olefin Homopolymerization and Copolymerization on Stereospecific Active Centers.- III-4-a Homopolymerization.- III-4-b Copolymerization.- III-5 Parameters Characterizing the Stereo regulative Ability of Active Centers.- III-6 Effect of Transition Metal Compounds on Catalyst Stereo specificity.- III-7 Effect of Organometallic Compounds on Catalyst Stereospecificity.- III-8 Temperature Effect on Catalyst Stereo specificity and the Reaction Pathway of the Propagation Step.- III-9 Role of Catalyst Modification.- III-9-a Catalyst Grinding.- III-9-b Organic Promoters.- III-9-c Inorganic Promoters.- III-9-d Supported Ziegler-Natta Catalysts.- III-10 Stereoregularity and Stereoelective Polymerization.- III-11 Stereoregularity of Monomer Sequences in Olefin Copolymers.- IV Inhomogeneity of Active Centers of Heterogeneous Ziegler Natta Catalysts.- IV-1 Distribution of Active Centers with Different Stereospecificity.- IV-1-a Existence and Models of Continuous Distribution.- IV-1-b Effect of Poisoning on Distribution of Active Center Stereospecificities.- IV-2 Molecular Weight Distribution of Polyolefins and the Distribution of Propagation Rate Constants.- IV-2-a Explanations for the Wide Molecular Weight Distributions of Polyolefins.- IV-2-b MWDs of Polypropylene Obtained at Low Temperature.- IV-3 Compositional Inhomogeneity of Olefin Copolymers and Active Center Distribution with Respect to Reactivity.- V Mechanism of Isospecific Olefin Polymerization.- V-1 Chemical Mechanism of Olefin Polymerization: Olefin Insertion Reaction into the—-Metal-Bond.- V-2 Intimate Mechanism of the Olefin Insertion Reaction.- V-2-a Olefin Coordination.- V-2-b Geometry of Olefin Coordination.- V-2-c Lability of the Transition Metal-Carbon Bond and the Insertion of Coordinated Olefin into it.- V-2-d Participation of Organometallic Compounds in the Polymerization Center.- V-2-e Cis-Insertion Reaction.- V-3 Molecular Orbital Calculations of the Propagation Step.- V-3-a Earlier Semi-empirical Calculations of the RTiCl4.Center.- V-3-b Hexa- vs. Pentacoordinated Centers: Calculations by CNDO Methods.- V-3-c Ab Initio Calculations of the Center Pentacoordinated.- V-3-d Molecular Orbital Calculations of a Center in u Crystal Lattice.- V-3-e Mechanism of Acetylene Polymerization.- V-4 Mechanism of Isospecific Chain Growth.- V-4-a Experimental Data on Isospecific Chain Propagation.- V-4-b Proposed Models of Isospecific Polymerization Centers.- V-5 Concluding Remarks on the Polymerization Mechanism.