New Methods of Polymer Synthesis

1 Developments in polymerization.- 1.1 Introduction.- 1.2 Radical addition polymerization.- 1.2.1 General features.- 1.2.2 Iniferters.- 1.2.3 Template polymerization.- 1.2.4 Ring-opening polymerization.- 1.2.5 Copolymerization.- 1.3 Ionic and coordination addition polymerization.- 1.3.1 General background and developments.- 1.3.2 Living anionic homo-and copolymerization of oxiranes.- 1.3.3 The activated monomer mechanism of oxirane polymerization.- 1.3.4 Living carbocationic polymerization of vinyl ethers.- 1.4 Stepwise polymerization.- 1.4.1 General background.- 1.4.2 Aromatic polyesters and polyamides.- 1.4.3 Polysulphones and polyketones.- 1.4.4 Starburst polymers: dendrimers and arborols.- 1.4.5 Biosynthetic routes to polymers.- References.- 2 Group transfer polymerizations.- 2.1 Introduction.- 2.1.1 Background.- 2.1.2 Terminology.- 2.1.3 Nucleophilic addition.- 2.1.4 Silyl ketene acetals.- 2.2 Features of group transfer polymerization.- 2.2.1 General features.- 2.2.2 Reaction conditions.- 2.2.3 Initiators.- 2.2.4 Catalysts.- 2.2.5 Monomers.- 2.2.6 Termination.- 2.2.7 Polymer microstructures.- 2.3 Kinetics and mechanism.- 2.3.1 Polymerization of methacrylates.- 2.3.2 Polymerization of acrylates.- 2.4 Aldol group transfer polymerization.- 2.5 Copolymers.- 2.5.1 Random copolymers.- 2.5.2 Block copolymers.- 2.5.3 Coupling.- 2.5.4 Other routes.- 2.6 Telechelics.- 2.7 Related and anionic polymerizations.- 2.8 Applications.- References.- 3 Ring-opening metathesis polymerization of cyclic alkenes.- 3.1 Scope of ring-opening metathesis polymerization.- 3.2 Monomers for ring-opening metathesis polymerization.- 3.3 Catalysts for the ring-opening polymerization of cycloalkenes.- 3.4 Mechanism of ring-opening metathesis polymerization.- 3.4.1 Site of olefin metathesis.- 3.4.2 Pairwise mechanisms.- 3.4.3 Non-pairwise mechanisms.- 3.4.4 Metallocyclobutanes.- 3.4.5 Transition metal carbenes.- 3.5 Molecular weight distribution in polyalkenylenes.- 3.6 Stereochemistry of ring-opening metathesis polymerization.- 3.6.1 Stereoisomerism of polyalkenylenes.- 3.6.2 Stereoisomerism in norbornene polymers.- 3.6.3 Substituted norbornenes.- 3.7 Thermodynamics of ring-opening polymerization.- 104 References.- 4 Transformation reactions.- 4.1 Introduction.- 4.2 Historical development of transformation reactions.- 4.3 Transformations between anionic and cationic polymerization.- 4.3.1 Anion to cation transformations.- 4.3.2 Cation to anion transformations.- 4.3.3 Anion to cation coupling reactions.- 4.4 Transformations between ionic and free radical polymerization.- 4.4.1 Anion to radical transformations.- 4.4.2 Cation to radical transformations.- 4.4.3 Radical to ionic transformations.- 4.5 Transformations involving other modes of polymerization.- 4.5.1 Anion to Ziegler-Natta transformations.- 4.5.2 Anion to metathesis transformations.- 4.5.3 Ziegler-Natta to radical transformations.- 4.5.4 Group transfer to radical transformations.- 4.5.5 Metathesis to aldol-group transfer transformations.- 4.5.6 Radical to active monomer transformations.- 4.5.7 Transformations between radical polymerization and polypeptide synthesis.- 4.6 Conclusions.- References.- 5 Chemical modification of preformed polymers.- 5.1 Introduction.- 5.2 Chemical reactions of polymers: general aspects.- 5.3 Modification of polymers.- 5.3.1 Modifications on the polymer main chain.- 5.3.2 Modifications of pendant groups.- 5.3.3 Miscellaneous systems.- 5.3.4 Concluding remarks.- References.- 6 Terminally reactive oligomers: telechelic oligomers and macromers.- 6.1 Introduction.- 6.2 The synthesis of terminally reactive oligomers.- 6.2.1 By anionic polymerization.- 6.2.2 By group transfer polymerization.- 6.2.3 By cationic polymerization.- 6.2.4 By radical polymerization.- 6.2.5 By stepwise polymerization.- 6.2.6 By controlled polymer chain scission.- 6.2.7 Modifications of end-groups of telechelic oligomers.- 6.3 Reactions and reactivity of telechelic oligomers and macromers.- 6.3.1 Telechelic oligomers.- 6.3.2 Macromers.- 6.4 Uses of terminally functionalized oligomers.- 6.4.1 Telechelic oligomers.- 6.4.2 Macromers.- References.