Front Cover 1
Stereospecific Polymerization of Isoprene 4
Copyright Page 5
Table of Contents 10
Foreword 6
Preface 8
PART I: DISSERTATION FOR THE DEGREE OF DOCTOR OF CHEMICAL ENGINEERING 14
LITERATURE DATA 16
Introduction 18
Chapter I. General comments on stereospecific polymerization 22
1. Research prior to the discovery of stereospecific polymerization 22
2. Structural characteristics 25
3. The main types of stereoregular polymers 26
4. General methods for the synthesis of stereoregular polymers 27
Chapter II. Stereospecific catalysts 32
A. Heterogeneous catalyst systems 32
B. Homogeneous catalyst systems 38
C. Catalysts effective in polar media 42
Chapter III. Mechanisms of stereospecificpolymerization 44
A. Free radical mechanisms 47
B. Ionic mechanisms 49
C. Mechanisms of polymerization using Ziegler-Natta catalystsystems 54
Chapter IV. Kinetics of stereospecificpolymerization 63
EXPERIMENTAL PART 74
Chapter I. Purification of the reagents usedin the stereospecific polymerizationof isoprene 76
A. Purification of isoprene 77
B. Solvent purification 88
C. Purification of catalyst components 91
D. Purification of nitrogen 93
Chapter II. Research on the stereospecificpolymerization of isoprene withheterogeneous catalyst systemsof the A1R3 + TiCl4 type 98
A. Polymerization of isoprene of over 99% purity 100
B. Polymerization of the ca. 25 % isoprene fraction 124
C. Some aspects of the kinetics of the stereospecificpolymerization of isoprene 143
Chapter III. Characterization of cis-1,4-polyisoprene 152
A. Physico-chemical characterization 152
B. Physico-mechanical characterization 159
Conclusions 165
PART II 170
Introduction 172
Chapter I. Pre-formed Ziegler-Natta-typecatalyst systems 174
1. Two-component A1R3 + TiCl4 catalyst systems 175
2. Modified A1R3 + TiCl4 catalyst systems 193
Chapter II. Stereospecific polymerization ofisoprene with pre-formed catalystcomplexes 205
1. Purity of polymerization systems 205
2. Some aspects of isoprene polymerization 207
3. Correlation between the structure and the technologicalbehaviour of polyisoprene 219
Chapter III. Deactivation of the catalyst complex 228
1. Deactivation of the catalyst complex without inactivation ofthe transition metal 229
2. Deactivation of the catalyst complex with inactivation of the transitionmetal 229
3. Deactivation of the catalyst complex in the absence ofpolyisoprene 231
4. Deactivation of the catalyst complex in the presence ofpolyisoprene 233
Chapter IV. The stabilization of polyisoprene 242
1. Autoxidation mechanisms 243
2. Relationships between structure and reactivity 245
3. Selection criteria for stabilizers 247
4. Mixtures of stabilizers 248
5. Estimation of the effectiveness of stabilizers 249
6. Macromolecular antioxidants 253
Chapter V. Recovery of polyisoprene fromsolution 259
Chapter VI. Characterization of cis-1,4-polyisoprene rubber by nuclearmagnetic resonance, electronmicroscopy and electron diffraction 267
1. Determination of the microstructure of eis- 1,4-polyisopreneby high-resolution nuclear magnetic resonance 267
2. Determination of glass-transition temperatures by electronspin resonance 269
3. Electron microscopy studies of natural rubber and syntheti ceis-1,4-polyisoprene 273
References 277
Index 292