Description During the past 30 years, the field of alkene polymerization over transition metal catalysts underwent several major changes:
1. The
list of commercial heterogeneous Ziegler-Natta catalysts for the synthesis of polyethylene and stereoregular polyolefins was completely
renewed affording an unprecedented degree of control over the polymer structure.
2. Research devoted to metallocene and other soluble
transition-metal catalysis has vastly expanded and has shifted toward complexes of transition metals with multidentate ligands.
3. Recent
developments in gel permeation chromatography, temperature-rising fractionation, and crystallization fractionation provided the first
reliable information about differences between various active centers in transition-metal catalysts.
4. A rapid development of high-resolution
13C NMR spectroscopy resulted in greatly expanded understanding of the chemical and steric features of polyolefins and alkene copolymers.
These developments require a new review of all aspects of alkene polymerization reactions with transition-metal catalysts. The first
chapter in the book is an introductory text for researchers who are entering the field. It describes the basic principles of polymerization
reactions with transition-metal catalysts, the types of catalysts, and commercially manufactured polyolefins.
The next chapter addresses
the principal issue of alkene polymerization catalysis: the existence of catalyst systems with single and multiple types of active centers.
The subsequent chapters are devoted to chemistry and stereochemistry of elemental reaction steps, structures of catalyst precursors
and reactions leading to the formation of active centers, kinetics of polymerization reactions, and their mechanisms.
Audience
Researchers, industrial laboratories Researchers, academia
Patent lawyers
Contents
Chapter 1. The beginner s course. General description of transition metal catalysts and catalytic polymerization reactions
1.1. Classifications
of transition metal catalysts
1.1.1. Components of transition metal catalysts
1.1.2. Catalyst classification based on solubility
1.2. Composition and structure Ziegler-Natta catalysts
1.2.1. Organoaluminum cocatalysts
1.2.2. Transition metal catalyst components
of Ziegler-Natta catalysts
1.2.3. Examples of Ziegler-Natta catalysts
1.2.3.1. Early and modern Ziegler-Natta catalysts
1.2.3.2.
Examples of catalysts for polymerization of ethylene and for copolymerization of ethylene with higher 1-alkenes
1.2.3.3. Examples
of catalysts for polymerization of propylene and higher alkenes
1.2.3.4. Catalysts for copolymerization of ethylene and propylene
1.3. Metallocene catalysts
1.4. Homogeneous catalysts containing non-metallocene complexes of early- and late-period transition metals
1.5. Chromium oxide catalysts
1.6. Main features of alkene polymerization reactions
1.6.1. Basic principles of polymerization kinetics
1.6.2. Copolymerization reactions of alkenes
1.6.3. Auto-copolymerization reactions and formation of polymer chains with long-chain
branches
1.6.4. Oligomerization reactions
1.6.5. Stereospecific alkene polymerization and stereoregular polyolefins
1.6.6. Nonuniformity
of active centers in transition metal catalysts
1.7. Classes of polymers produced with transition metal catalysts
1.7.1. Linear polyethylene
and semi-crystalline ethylene copolymers
1.7.1.1. Catalysts and technologies of manufacture of polyethylene resins
1.7.1.2. Control
of polyethylene properties and its commercial uses
1.7.2. Ethylene/propylene elastomers
1.7.3. Poly(olefins)
1.7.3.1. Propylene
polymers and copolymers
1.7.3.2. Commercial polymers of higher 1-alkenes
1.7.3.3. Poly(cycloalkenes) and cycloalkene copolymers
1.7.3.4. Syndiotactic polystyrene
Chapter 2. Single-center and multi-center polymerization catalysis
2.1. Definition of a single
type of active center
2.2. Molecular weight distribution of polymers produced with single-center catalysts
2.2.1. Molecular weight
distribution, theory
2.2.2. Experimental techniques for the analysis of molecular weight distribution, gel permeation chromatography
2.2.3. Experimental techniques for the measurement of molecular weight distribution used in industry
2.2.4. Experimental techniques
for the analysis of molecular weight distribution, gas chromatography
2.3. Structural uniformity of polymers and copolymers produced
with single-center catalysts
2.3.1. Structural uniformity of polymers and copolymers, theory
2.3.2. Experimental techniques for the
analysis of steric structure of alkene homopolymers and compositional distribution of copolymers
2.3.2.1. Early fractionation methods
2.3.2.2. Preparative fractionation methods
2.3.2.3. Automated methods, analytical Tref and Crystaf methods
2.3.2.4. Melting
point measurement, differential scanning calorimetry
2.4. Examples of polymers and copolymers produced with single-center catalysts
2.4.1. Molecular weight distribution of polymers and produced with single-center catalysts
2.4.2. Structural uniformity of alkene
polymers produced with single-center catalysts
2.5. Examples of polymers and copolymers produced with multi-center catalysts
2.5.1.
Molecular weight distribution of polymers produced with multi-center catalysts
2.5.1.1. Heterogeneous Ziegler-Natta catalysts
2.5.1.2.
Metallocene catalysts
2.5.1.3. Non-metallocene homogeneous catalysts
2.5.1.4. Chromium-based and multi-component catalysts
2.5.2.
Steric structure of alkene homopolymers, different definitions of stereoregularity
2.5.3. Steric structure of alkene homopolymers
produced with multi-center catalysts
2.5.4. Compositional distribution of copolymers produced with multi-center catalysts
Chapter
3. Chemistry and stereochemistry of polymerization and copolymerization reactions with transition metal catalysts
3.1. Chemistry and
stereochemistry of polymerization reactions
3.1.1. Definition of regioselectivity
3.1.2. Stereospecificity in alkene polymerization
reactions
3.1.3. Statistics of predominantly stereoregular polymers
3.1.3.1. Isospecific catalysis, site-control (enantiomorphic)
mechanism
3.1.3.2. Isospecific catalysis, chain-end stereocontrol mechanism
3.1.3.3. Syndiospecific catalysis, site-control (enantiomorphic)
mechanisms
3.1.3.4. Syndiospecific catalysis, chain-end stereocontrol mechanism
3.1.3.5. Mixed statistical schemes in stereospecific
polymerization reactions
3.2. Heterogeneous titanium- and vanadium-based Ziegler-Natta catalysts
3.2.1. Chemistry of chain initiation,
propagation, and transfer reactions
3.2.1.1. Chain growth reactions
3.2.1.1.1. Standard chain growth reactions
3.2.1.1.2. Unconventional
chain growth reactions
3.2.1.2. Chain transfer and chain initiation reactions
3.2.1.2.1. Chain transfer reactions after primary
insertion of the last monomer unit and the following chain initiation reactions
3.2.1.2.2. Initial chain initiation reactions
3.2.1.2.3. Chain transfer reactions after secondary insertion of the last monomer unit and the following chain initiation reactions
3.2.2. Reactivities of alkenes in polymerization reactions
3.2.2.1. Reactivities of alkenes in chain growth reactions
3.2.2.2.
Reactivities of alkenes in chain initiation reactions
3.2.3. Stereospecificity of titanium-based polymerization catalysts
3.2.3.1.
Two alternative models of predominantly isotactic polymer chains
3.2.3.2. Stereospecificity in chain growth reactions
3.2.3.3.
Stereochemistry of chain initiation reactions
3.3. Metallocene catalysts
3.3.1. Chemistry of chain initiation, propagation, and transfer
reactions
3.3.1.1. Chain growth reactions
3.3.1.1.1. Standard chain growth reactions
3.3.1.1.2. Chain insertion/isomerization
reactions
3.3.1.1.3. Chain insertion reactions in polymerization of – ?z? -dienes
3.3.1.2. Chain transfer and chain initiation
reactions
3.3.1.2.1. Chain transfer reactions after primary insertion of the last monomer unit and the following chain initiation
reactions
3.3.1.2.2. Initial chain initiation reactions
3.3.1.2.3. Chain transfer after secondary insertion of the last monomer
unit and the following chain initiation reactions
3.3.1.2.4. Generation of molecular hydrogen by metallocene catalysts
3.3.2. Stereochemistry
of chain growth reactions
3.3.2.1. Catalysts based on nonbridged bis-metallocene and monometallocene complexes
3.3.2.2. Isospecific
catalysts based on bridged bis-metallocene complexes
3.3.2.2.1. Bis-metallocene complexes of C2 symmetry
3.3.2.2.2. Asymmetric
bis-metallocene complexes
3.3.2.3. Syndiospecific catalysts based on bridged bis-metallocene complexes
3.3.2.4. Hemi-isospecific
metallocene catalysts
3.3.3. Polymerization and copolymerization reactions of styrene
3.4. Homogeneous catalysts based on early-period
transition metals
3.4.1. Complexes with monodentate ligands
3.4.2. Complexes with bidentate, tridentate, and tetradentate ligands
3.4.3. Chain insertion reactions in polymerization of alkenes with internal double bonds
3.4.4. Styrene polymerization and copolymerization
reactions
3.5. Homogeneous catalysts based on late-period transition metals
3.5.1. Regiochemistry of chain initiation and chain growth
reactions
3.5.2. Stereochemistry of chain growth reactions
3.5.3. Chain-isomerization reactions
3.6. Chromium-based catalysts
3.6.1.
Chromium oxide catalysts
3.6.2. Organochromium catalysts
3.7. Stereoselective and stereoelective polymerization reactions of branched
1-alkenes
3.7.1. Stereoselective polymerization reactions with Ziegler-Natta catalysts
3.7.2. Stereoelective polymerization reactions
with Ziegler-Natta and metallocene catalysts
3.8. Copolymerization reactions of alkenes
3.8.1. Copolymerization reactions, reactivity
ratios for various alkene pairs
3.8.2. Statistical description of copolymer structure in terms of block length
3.8.3. Statistical
description of copolymer structure suitable for NMR analysis
3.8.4. Auto-copolymerization reactions and long chain branching in alkene
polymers
Chapter 4. Synthesis, chemical composition, and structure of transition metal catalysts for alkene polymerization
4.1. Early
solid Ziegler-Natta catalysts
4.2. Supported Ziegler-Natta catalysts for homopolymerization and copolymerization of ethylene
4.2.1.
Titanium-based Ziegler-Natta catalysts
4.2.1.1. General features of catalysts for ethylene/1-alkene copolymerization
4.2.1.2.
Catalysts produced from soluble MgCl2 complexes
4.2.1.3. Catalysts produced by synthesis of MgCl2
4.2.1.4. Specialized Ti-based
catalysts for ethylene polymerization
4.2.1.5. Pseudo-homogeneous Ti-based catalysts for ethylene polymerization
4.2.2. Vanadium-based
Ziegler-Natta catalysts
4.2.3. Chromium-based catalysts
4.2.3.1. Chromium oxide catalysts
4.2.3.2. Supported organochromium catalysts
4.3. Supported Ziegler-Natta catalysts for polymerization of propylene and higher 1-alkenes
4.3.1. Catalysts based on – -TiCl3
4.3.2.
Catalysts supported on MgCl2
4.3.2.1. Catalysts produced by milling MgCl2
4.3.2.2. Catalysts produced from soluble MgCl2 complexes
4.3.2.3. Catalysts produced by synthesis of MgCl2
4.3.2.4. Effects of Modifiers I and II on catalyst performance
4.3.2.5. Catalysts
for synthesis of atactic polypropylene
4.4. Chemical composition of solid components and cocatalyst mixtures of Ti-based Ziegler-Natta
catalysts
4.4.1. Supported TiCl4/MgCl2 catalysts, catalyst models
4.4.2. Supported TiCl4/MgCl2 catalysts, structure of solid components
4.4.2.1. Structure of MgCl2 support
4.4.2.2. Esters in catalysts
4.4.2.3. Ti species in catalysts
4.4.3. Cocatalyst compositions,
reactions of AlR3 and Modifiers II
4.4.3.1. Reactions of AlR3 and esters of aromatic acids
4.4.3.2. Reactions of AlR3 with alkoxysilanes
and diethers
4.5. Reactions leading to formation of active centers in Ziegler-Natta catalysts
4.5.1. Early catalyst compositions,
reactions between MCl3 and AlR3
4.5.2. Supported catalyst compositions, reactions between catalysts and cocatalysts
4.5.2.1. Reactions
in model catalyst systems
4.5.2.2. Reactions between cocatalysts and Modifiers I
4.5.2.3. Complexes of MgCl2 and solid catalysts
with silanes
4.5.2.4. Valence state of titanium atoms
4.5.2.5. Aluminum species in solid catalysts
4.5.2.6. Reactions in vanadium-based
catalysts
4.6. Metallocene catalysts
4.6.1. Types of metallocene complexes used in polymerization catalysts
4.6.2. Cocatalysts for
metallocene complexes
4.6.1.1. Cocatalysts in early metallocene catalysts
4.6.2.2. Alkylalumoxanes
4.6.2.3. Analogs of alkylalumoxanes
4.6.2.4. Ion-forming cocatalysts
4.6.3. Activity of metallocene catalysts
4.6.4. Stereospecific metallocene catalysts
4.6.5.
Reactions leading to active centers in metallocene catalysts
4.7. Non-metallocene homogeneous catalysts
4.7.1. Complexes of early-period
transition metals
4.7.1.1. Complexes with monodentate ligands
4.7.1.2. Complexes with bidentate ligands
4.7.1.3. Complexes with
tetradentate ligands
4.7.2. Complexes of late-period transition metals
4.7.2.1. Complexes with bidentate ligands
4.7.2.2. Complexes
with tridentate ligands
4.8. Supported homogeneous catalysts
4.9. Bicomponent catalysts
4.9.1. Catalysts for polymers with a broad
molecular weight distribution
4.9.2. Catalysts for synthesis of block-copolymers and branched polymers
4.9.3. Binary Ziegler-Natta/metallocene
systems
4.10. Catalysts for stereospecific polymerization of styrenes
4.10.1. Isospecific catalysts
4.10.2. Syndiospecific catalysts
Chapter 5. Kinetics of alkene polymerization reactions with transition metal catalysts
5.1. Two aspects of polymerization kinetics
5.2. Role of diffusion in alkene polymerization reactions
5.3. Formal kinetic description of alkene polymerization reactions with transition
metal catalysts
5.3.1. Homopolymerization reactions
5.3.2. Copolymerization reactions
5.3.3. Stopped-flow kinetic method and living-chain
polymerization reactions
5.4. Polymerization reactions with metallocene catalysts
5.4.1. General kinetic behavior
5.4.2. Detailed
kinetic studies
5.4.2.1. Ethylene polymerization reactions
5.4.2.2. Propylene polymerization reactions
5.4.2.3. Polymerization
reactions of higher 1-alkenes and styrenes
5.4.3. General kinetic studies, effects of reaction parameters
5.4.3.1. Polymerization
reactions with ionic metallocene catalysts
5.4.3.2. Polymerization reactions with MAO-activated metallocene catalysts
5.4.3.2.1.
Acceleration period
5.4.3.2.2. Stationary period, effects of reaction parameters
5.4.3.2.3. Catalyst deactivation
5.4.3.2.4.
Poisoning of active centers in metallocene catalysts
5.4.3.2.5. Number of active centers in metallocene catalysts
5.5. Polymerization reactions with non-metallocene homogeneous catalysts
5.5.1. Living-chain polymerization reactions
5.5.2. Kinetics of oligomerization
reactions
5.5.3. Limiting kinetic steps in polymerization reactions
5.5.4. Single- vs. multi-center polymerization catalysis
5.6.
Synthesis of alkene block-copolymers
5.6.1. Living-chain polymerization reactions and synthesis of alkene block-copolymers
5.6.2.
Synthesis of alkene block-copolymers using chain transfer agents
5.7. Polymerization reactions with solid and supported Ziegler-Natta
catalysts
5.7.1. Ethylene polymerization reactions
5.7.1.1. Ethylene homopolymerization reactions
5.7.1.1.1. General kinetic
behavior
5.7.1.1.2. Effects of reaction parameters
5.7.1.2. Ethylene/1-alkene copolymerization reactions
5.7.1.3. General kinetic
scheme of ethylene polymerization reactions
5.7.2. Propylene polymerization reactions
5.7.2.1. General kinetic behavior
5.7.2.2.
Effects of reaction parameters
5.7.2.3. Catalyst modifiers, selective poisoning of active centers
5.7.2.4. Nonselective catalyst
poisons
5.7.2.5. Other kinetic features of propylene polymerization reactions
5.7.2.6. Comparison of ethylene and propylene copolymerization
kinetics
5.7.3. Polymerization reactions of higher 1-alkenes and styrene
5.7.4. Estimation of number of active centers in Ziegler-Natta
catalysts
5.7.4.1. Kinetic approaches to estimation of number of active centers
5.7.4.2. Poisoning of active centers and estimation
of their number
5.7.4.2.1. CO and CO2 as poisons, step-poisoning experiments
5.7.4.2.2. CO and CO2 as poisons, 14C-labeling
5.7.4.2.3. Allene and CS2 as poisons
5.7.4.2.4. Destructive poisons, alcohols
5.7.4.2.5. Destructive poisons, acid chlorides
5.7.4.2.6. Other C* measurement methods
5.7.5. General classification of active centers in heterogeneous Ziegler-Natta catalysts
5.7.6. Physical effects in polymerization reactions with heterogeneous Ziegler-Natta catalysts
5.8. Polymerization reactions with
pseudo-homogeneous catalysts
5.9. Polymerization reactions with chromium oxide catalysts
5.9.1. General kinetic behavior
5.9.2.
Effects of reaction parameters
Chapter 6. Active centers in transition metal catalysts and mechanisms of polymerization reactions
6.1.
Catalysts derived from metallocene complexes
6.1.1. Formation and structure of active centers
6.1.1.1. Catalysts utilizing ion-forming
cocatalysts
6.1.1.2. Catalysts derived from constrained-geometry complexes
6.1.1.3. Early metallocene catalysts
6.1.1.4. Metallocene
catalysts utilizing MAO as a cocatalyst
6.1.1.5. Chemistry and mechanism of catalyst deactivation reactions
6.1.2. Mechanism of
alkene polymerization reactions, experimental data and theoretical analysis
6.1.2.1. Mechanism of normal chain growth and chain transfer
6.1.2.1.1. The C=C bond coordination stage
6.1.2.1.2. The C=C bond insertion step in model systems
6.1.2.1.3. C=C bond insertion
reactions in metallocenium ions
6.1.2.1.4. The C=C bond insertion step into the [Cp]Zr+?{H bond
6.1.2.1.5. Theoretical analysis
of C=C bond insertion steps
6.1.2.1.6. Mechanism of chain transfer reactions
6.1.2.1.7. Agostic interactions in active centers
6.1.2.1.8. Poisoning of active centers in metallocene catalysts
6.1.2.2. Mechanisms of chain isomerization
6.1.3. Stereospecificity
of active centers in metallocene catalysts
6.1.3.1. Non-bridged metallocene complexes.
6.1.3.2. Isospecific bridged metallocene
complexes
6.1.3.2.1. Active centers derived from complexes of C2 symmetry
6.1.3.2.2. Centers of C2 symmetry, mechanism of isospecific
chain growth
6.1.3.2.3. Centers of C2 symmetry, mechanisms of steric errors
6.1.3.2.4. Active centers derived from complexes
of C1 symmetry
6.1.3.2.5. Centers of C1 symmetry, mechanism of isospecific chain growth
6.1.3.3. Syndiospecific bridged metallocene
complexes
6.1.3.3.1. Centers of C2 symmetry, mechanism of syndiospecific chain growth 6.1.3.3.2. Centers of Cs symmetry, mechanism
of steric errors
6.1.3.3.3. Centers of C1 symmetry, mechanism of syndiospecific chain growth
6.1.4. Mechanism of styrene polymerization
6.2. Non-metallocene homogeneous catalysts
6.2.1. Vanadium-based catalysts
6.2.2. Ni ylide catalysts for ethylene oligomerization
6.2.3. Catalysts derived from complexes with (imino)pyridyl ligands
6.2.4. Catalysts derived from complexes with – -diimine ligands
6.2.4.1. Chain growth mechanism
6.2.4.2. Chain isomerization mechanism
6.3. Active enters in heterogeneous Ziegler-Natta catalysts
6.3.1. Formation of active centers
6.3.2. Structural features of active centers
6.3.3. Poisoning of active centers
6.3.4. Physical
observations, position of active centers on catalyst surface
6.3.5. Mechanism of alkene polymerization reactions with Ziegler-Natta
catalysts
6.3.5.1. Experimental data
6.3.5.2. Models of active centers, theoretical analysis
6.3.6. Stereospecificity of active
centers
6.3.6.1. Experimental data
6.3.6.2. Models of isospecific centers, theoretical results
6.4. Chemical nature of active
enters in chromium oxide catalysts
6.4.1. Formation and structure of active centers
6.4.2. Mechanism of alkene polymerization
6.4.2.1.
Experimental data
6.4.2.2. Theoretical results
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