Polymerization group transfer method

A brief review has appeared covering the use of metal-free initiators in living anionic polymerizations of acrylates and a comparison with Du Font s group-transfer polymerization method (149). Tetrabutylammonium thiolates mn room temperature polymerizations to quantitative conversions yielding polymers of narrow molecular weight distributions in dipolar aprotic solvents. Block copolymers are accessible through sequential monomer additions (149—151) and interfacial polymerizations (152,153). 

Webster OW (2004) Group transfer polymerization mechanism and comparison with other methods for controlled polymerization of acrylic monomers. In New synthetic methods. Advances in polymer science, vol 167. Springer, Berlin, pp 1-34... 

Webster, O. IV Group Transfer Polymerization Mechanism and Comparison with Other Methods of Controlled Polymerization of Acrylic Monomers. Vol. 167, pp. 1-34. 

Webster OW, Anderson BC (1992) Group transfer polymerization, in new methods for polymer synthesis. Mijs WJ Ed, Plenum, p.l... 

Most of the methods for synthesizing block copolymers were described previously. Block copolymers are obtained by step copolymerization of polymers with functional end groups capable of reacting with each other (Sec. 2-13c-2). Sequential polymerization methods by living radical, anionic, cationic, and group transfer propagation were described in Secs. 3-15b-4, 5-4a, and 7-12e. The use of telechelic polymers, coupling and transformations reactions were described in Secs. 5-4b, 5-4c, and 5-4d. A few methods not previously described are considered here. 

Stars with high arm numbers are commonly prepared by the arm-first method. This procedure involves the synthesis of living precursor arms which are then used to initiate the polymerization of a small amount of a difunctional monomer, i.e., for linking. The difunctional monomer produces a crosslinked microgel (nodule), the core for the arms. The number of arms is a complex function of reaction variables. The arm-first method has been widely used in anionic [3-6,32-34], cationic [35-40], and group transfer polymerizations [41] to prepare star polymers having varying arm numbers and compositions. 

Group Transfer Polymerization Mechanism and Comparison with Other Methods... 

Eastmond GC, Webster OW (1991) Group transfer polymerization. In Ebdon JR (ed) New methods of polymer synthesis. Blackie, London, p 24... 

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