Polymerization surface-initiated

Wang J, Gibson MI, Barbey R, Xiao SJ, Klok HA (2009) Nonfouling polypeptide brushes via surface-initiated polymerization of N-epsilon-oligo(ethylene glycol)succinate-L-lysine N-carboxyanhydride. Macromol Rapid Commun 30 845-850... 

Surface-Initiated Polymerization I Volume Editor Jordan, R. 

Wang, D., et al., Graphene functionalized with azo polymer brushes Surface-initiated polymerization andphotoresponsiveproperties. Advanced Materials, 2011. 23(9) p. 1122-1125. 

Fig. 9.19 Preparation of polymer brushes on solid surfaces by a) chemical grafting of end-functionalized linear polymers or selective adsorption of asymmetric block copolymers and b) by surface-initiated polymerization (SIP) using initiator functions on the solid surface. The depicted SAM bearing to-functionalities...

In this method, a reactive group on the surface initiates the polymerization, and the propagating polymer chain grows from the surface (Fig. 9.19b). In principle, it can be employed with all polymerization types, and a number of papers have reported high amounts of immobihzed polymer using surface-initiated polymerization with various initiator/monomer systems. If controlled or Hving polymerization techniques are used, block copolymer or end-functionahzed polymer brush systems can be prepared in consecutive reaction steps (Fig. 9.19c). 

Surface-initiated Polymerization Using Living Ionic Polymerization... 

The first report on living carbocationic surface-initiated polymerization (LCSIP) using a defined surface modification is by Vidal and Kennedy [268-270]. They prepared poly(isobutene) (PIB) brushes from silica surfaces using a silane functionalized benzylchloride activated by a Lewis acid. 

The same aplies to polymer brushes. The use of SAMs as initiator systems for surface-initiated polymerization results in defined polymer brushes of known composition and morphology. The different polymerization techniques, from free radical to living ionic polymerizations and especially the recently developed controlled radical polymerization allows reproducible synthesis of strictly linear, hy-perbranched, dentritic or cross-linked polymer layer structures on solids. The added flexibility and functionality results in robust grafted supports with higher capacity and improved accessibility of surface functions. The collective and fast response of such layers could be used for the design of polymer-bonded catalytic systems with controllable activity. 

Advincula R. Polymer Brushes by Anionic and Cationic Surface-Initiated Polymerization (SIP). Vol. 197, pp. 107-136. 

Finally, I would Hke to thank all authors for their time and effort to make a state-of-the-art overview of surface-initiated polymerization possible. An edited book is only as good as its contributions and I had the privilege to compile contributions of the highest quality. 

Fig. 10 Illustrations of the microchannel confined surface-initiated polymerization (p-SIP) route for producing gradient polymer brush libraries a route for making polymer molecular weight and block copolymer libraries b route for making statistical copolymer libraries. Red arrows show the flow of monomer solution from a syringe pump used to gradually fill the microchannel. See text for details...

Xu C, Wu T, Drain CM, Batteas JD, Beers KL (2005) MicroChannel confined surface-initiated polymerization. Macromolecules 38 6... 

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