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Atom Transfer Radical Polymerization
Krzysztof Matyjaszewski* and Jianhui Xia
Contents
I. Introduction 2921
II. Mechanistic Understandings of Atom Transfer
Radical Polymerization
2923
A. Components 2923
1. Monomers 2923
2. Initiators 2924
3. Catalysts 2924
4. Solvents 2924
5. Temperature and Reaction Time 2925
6. Additives 2925
B. Typical Phenomenology 2925
1. Kinetics 2925
2. Molecular Weight 2926
3. Molecular Weight Distribution 2926
4. Normal and Reverse ATRP 2927
5. Experimental Setup 2927
6. Catalyst Homogeneity 2927
7. Summary and Outlook 2928
C. ATRP Monomers 2928
1. Styrenes 2928
2. Acrylates 2929
3. Methacrylates 2929
4. Acrylonitrile 2930
5. (Meth)acrylamides 2930
6. (Meth)acrylic Acids 2931
7. Miscellaneous Monomers 2931
8. Summary and Outlook 2931
D. ATRP Initiators 2932
1. Halogenated Alkanes 2932
2. Benzylic Halides 2932
3. R-Haloesters 2933
4. R-Haloketones 2933
5. R-Halonitriles 2934
6. Sulfonyl Halides 2934
7. General Comments on the Initiator
Structure in ATRP
2934
8. Summary and Outlook 2935
E. Transition-Metal Complexes 2935
1. Group 6: Molybdenum and Chromium 2935
2. Group 7: Rhenium 2936
3. Group 8: Ruthenium and Iron 2936
4. Group 9: Rhodium 2938
5. Group 10: Nickel and Palladium 2938
6. Group 11: Copper 2939
7. Summary and Outlook 2940
F. Ligand 2941
1. Nitrogen Ligands 2941
2. Phosphorus Ligands 2941
3. Miscellaneous Ligands 2942
4. Summary and Outlook 2942
G. Additives 2942
H. Catalyst Structure 2943
I. Mechanism 2945
J. Overall Elementary Reactions 2947
III. Materials Made by ATRP 2949
A. Functionality 2949
1. Monomer Functionality 2949
2. Initiator Functionality 2952
3. Chain End Functionality 2955
4. Summary and Outlook 2957
B. Composition 2957
1. Gradient/Statistical Copolymers 2958
2. Block Copolymers 2960
3. Inorganic/Organic Hybrids 2969
4. Summary and Outlook 2970
C. Topology 2972
1. Graft Copolymers 2972
2. Grafts from Surfaces 2977
3. Star Polymers 2978
4. Hyperbranched Polymers 2981
5. Summary and Outlook 2983
IV. Conclusions 2983
V. Acknowledgment 2985
VI. References 2985
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