Polymers with reactive functional groups anionic polymerization

Transformation of Anionic Polymerization into Cationic Polymerization. Richards et al. (26. 27, 73-75) proposed several methods for the transformation of a living anionic polymeric chain end into a cationic one. Such a process requires three distinct stages polymerization of a monomer I by an anionic mechanism, and capping of the propagating end with a suitable but potentially reactive functional group isolation of polymer I, dissolution in a solvent suitable for mechanism (2), and addition of monomer II and reaction, or change of conditions, to transform the functionalized end into propagating species II that will polymerize monomer II by a cationic mechanism (73). 

The broad range of control of solution polymer structure and macrostructure of styrene-butadiene rubbers that is only possible using lithium catalysts was discussed in Section 2. We have seen how the microstructure of the butadiene units in the chain and comonomer sequence distribution can be controlled with the addition of polar modifiers and/or variations in pol5onerization process variables. Additionally, the unique control of macrostructure features and the new possibilities offered by reactive functional groups were discussed as part of the molecular engineering capabilities of solution anionic polymerizations. 

Anionic polymerization of functionalized cyclotrisiloxanes is a good method for the synthesis of well-defined functionalized polysiloxane with control of molecular mass, polydispersion, and density and arrangement of functional groups. These polymers may serve as reactive blocks for the building of macromolecular architectures, such as all-siloxane and organic-siloxane block and graft copolymers, star-, comb- and dendritic-branched copolymers and various polysiloxane-inorganic solid hybrids. 

Reactive chains can be obtained by anionic polymerization, followed by attachment of a reactive end-group. This route yields nearly monodisperse polymers with functional groups at their ends, polymers that are very well suited for systematic studies. The synthesis can be quite elaborate, and, for longer chains, the completeness of the end-functionalization is difficult to verify. If the mono-dispersity and the control of the molecular weight of the polymer are not crucial or not possible, more common techniques can be used. They involve either the free-radical synthesis of a polymer incorporating a small fraction of reactive comonomers that will then be distributed along the chain, or the random functionalization of the polymer in the melt (using a free-radical initiator) after the... 

B-90 and B-91, respectively.390 Another route coupled with cationic ring-opening polymerizations is accomplished for polymer B-92 with the use of a hydroxyl-functionalized initiator with a C—Br terminal, where the OH group initiates the cationic polymerizations of 1,3-dioxepane in the presence of triflic acid.329 Polyethylene oxide)-based block copolymers B-93 are obtained by living anionic polymerization of ethylene oxide and the subsequent transformation of the hydroxyl terminal into a reactive C—Br terminal with 2-bromopropionyl bromide, followed by the copper-catalyzed radical polymerization of styrene.391... 

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