Arborescent polystyrene, synthesis

Scheme 30.14 Arborescent polystyrene synthesis linear substrate functionalization by chloromethylation (1) or acetylation (2), and coupling with living polystyrene to yield a GO molecule (3).

Scheme 6.2 Arborescent polystyrene synthesis by grafting onto chloromethylated polystyrene.

Scheme 30.17 One-pot synthesis of arborescent polystyrene by a semibatch process with mixed monomer additions. Source Reproduced with permission from Yuan Z, Gauthier M. Macromolecules 2063 2006 39 [114]. Copyright 2006 American Chemical Society.

Gauthier M, Li J, Dockendoiff J (2003) Arborescent polystyrene-graft-poly(2-vinylpyridine) copolymers as unimolecular micelles. Synthesis from acetylated substrates. Macromolecules... 

The step-wise synthesis of arborescent polymers, while able to generate large amounts of materials in good yield, requires isolation and purification of the crude product prior to substrate functionalization. For less-demanding applications not requiring stringent removal of the linear polymer contaminant, a one-pot method was recently developed by Yuan and Gauthier (2006) for the synthesis of arborescent polystyrene without isolation of the reaction intermediates. 

Kee, R.A. and Gauthier, M. (2002) Arborescent polystyrene-gra -poly(2-vinylpyridine) copolymers Synthesis and enhanced polyelectrolyte effect in solution. Macromolecules, 35,6526-6532. 

Li, J., Teertstra, S.J., Gauthier, M. et al (2004) Synthesis of arborescent polystyrene-grayi-polyisoprene copolymers using acetylated substrates. Macromolecules, 37,795-802. 

Munam, A. and Gauthier, M. (2008) Large-scale synthesis of arborescent polystyrenes. Journal of Polymer Science, Part A Polymer Chemistry, 46,5742-5751. 

Puskas, J.E. Biomacromolecular engineering Design, S3mthesis and characterization. One-pot synthesis of block copolymers of arborescent polyisobutylene and polystyrene, Polym. Adv. TechnoL, 7, 1, 2006. 

Puskas, J.E. et al. Synthesis and characterization of novel dendritic (arborescent) polyisobutylene-polystyrene thermoplastic elastomers, J. Polym. Set A, 43, 1811, 2005. 

This chapter focuses on the latest efforts in our laboratory aimed at the synthesis and the physical characterization of arborescent polymers. The synthesis of arborescent styrene and isoprene homopolymers is discussed, together with copolymers incorporating a polystyrene substrate grafted with side chains of different compositions such as poly(2-vinylpyridine). 

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