Anionic-cationic synthesis termination reactions

The use of polymeric initiators or coinitiators to induce the polymerisation of a second monomer by a cationic mechanism is a particularly attractive possibility, since it would permit the synthesis of block and graft copolymers. The search for adequate systems in this context has been intensive, but only very recently has it met with some success, and this is far from being as spectacular as the achievements obtained in the same area with anionic systems. The main difficulties to be surmcwntedhave been discussed in the general introduction to this review (see Chap. I), and have to do with the ubiquity of transfer and termination reactions in cationic polymerisation. Nevertheless, the advances of the last few years seem encouraging and one would expect that the near future will provide considerable progress, both quantitative and qualitative. 

Anionic-Cationic (Ion Coupling) Methods. Anionic-cationic termination reactions have been reported (57) to be useful in the synthesis of block polymers of the type THF-S and THF-S-THF (Reaction 13) ... 

Since the discovery of living polymerizations by Swarc in 1956 [1], the area of synthesis and application of well-defined polymer structures has been developed. The livingness of a polymerization is defined as the absence of termination and transfer reactions during the course of the polymerization. If there is also fast initiation and chain-end fidelity, which are prerequisites for the so-called controlled polymerization, well-defined polymers are obtained that have a narrow molar mass distribution as well as defined end groups. Such well-defined polymers can be prepared by various types of living and controlled polymerization techniques, including anionic polymerization [2], controlled radical polymerization [3-5], and cationic polymerization [6, 7]. 

A similar approach has been also used for the synthesis of covalently linked DHBCs. Polysaccharide based DHBCs were prepared by end-to-end eoupling of two readily available biocompatible water-soluble homopolymers [35]. The synthesis was a two step reaction where a) a terminal aldehyde group of a dextran homopolymer was oxidized and b) a monoamine end functionalized PEG reaeted with the oxidized dextran, via a lactone aminolysis reaction. Interestingly, the obtained polymer could be chemically modified, in a controlled way, in order to produce neutral-cationic or neutral-anionic DHBCs. 

---