Telechelics synthetic techniques

ADMET is quite possibly the most flexible transition-metal-catalyzed polymerization route known to date. With the introduction of new, functionality-tolerant robust catalysts, the primary limitation of this chemistry involves the synthesis and cost of the diene monomer that is used. ADMET gives the chemist a powerful tool for the synthesis of polymers not easily accessible via other means, and in this chapter, we designate the key elements of ADMET. We detail the synthetic techniques required to perform this reaction and discuss the wide range of properties observed from the variety of polymers that can be synthesized. For example, branched and functionalized polymers produced by this route provide excellent models (after quantitative hydrogenation) for the study of many large-volume commercial copolymers, and the synthesis of reactive carbosilane polymers provides a flexible route to solvent-resistant elastomers with variable properties. Telechelic oligomers can also be made which offer an excellent means for polymer modification or incorporation into block copolymers. All of these examples illustrate the versatility of ADMET. 

The introduction of the concept of Click chemistry, as a family of organic reactions that fulfil certain criteria drawn by Sharpless and coworkers in 2001 [194], has indeed captured the attention of synthetic chemists in the field of postpolymerization modification towards glycopolymer synthesis [32]. The most widely employed Click reaction is the CuAAC reaction. ATRP has been used extensively in conjunction with CuAAC Click chemistry. This is probably because both techniques are mediated by Cu(I). Moreover, the halogen chain ends of polymers prepared using ATRP can easily be transformed into azides to form what is known as azido-telechelic polymers. Many examples of glycopolymers prepared by the combination of Click chemistry and ATRP have been reported [32, 99]. 

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