Polymer grafting graft from” strategy

Figure 1.2 Functional polymer layers on surfaces produced with (a) grafting to and (b) grafting from strategies, (a) In grafting-to processes, preformed polymer chains containing a linker group (B) are chemically bound to anchor groups (A), (b) In grafting-from, polymerization of a monomer (M) is started from initiators (I) bound to the surface.

Scheme 30.20 Preparation of a heterofunctional hyperbranched polymer via the self-condensing ATRP of an azide-functional inimer and subsequent click coupling combined with the grafting-from strategy to afford multihetero-arm hyperbranched brushes. Reproduced with permission from Ref [149] 2009, The Royal Society of Chemistry.

Polymer Grafting Based on Graft From Strategy... 

Graft copolymers were prepared by both classical strategies, i.e., from enzymatically obtained macromonomers using subsequent chemical polymerization and by enzymatic grafting from hydroxy-functional polymers. 

Graft copolymers were prepared by both classical strategies, that is, from enzymatically obtained macromonomers by subsequent chemical polymerization and by enzymatic grafting from hydroxyl functional polymers. Kalra et al. studied the synthesis of PPDL graft copolymers from macromonomers, which were obtained by the enzymatic ROP of pentadecalactone (PDL) from hydroxyethyl methacrylate (HEMA) and polyethylene glycol) methacrylate (PEGMA) [40]. Subsequently graft copolymers were obtained by free radical polymerization of the macromonomers. A similar approach was published by Srivastava for the HEMA-initiated enzymatic ROP of CL and subsequent free radical polymerization [41]. 

Three main strategies have been successfully developed for the synthesis of cylindrical polymer brushes grafting through, grafting to, and grafting from. Scheme 8 shows the processes for each preparation strategy. 

Part of grafting strategies can also be used in association with photoinduced polymerization. As previously stated, grafting from methodology consists of polymerization of monomers initiated from active sites distributed along a polymer backbone or a surface. Photoinitiated polymerizations can well be adapted to this... 

Recently, we explored strategies for binding spiropyran moieties to structured brushes grafted from ETFE and Teflon (PTFE) surfaces in order to obtain light-sensitive structured polymer surfaces [18]. We focused on post-polymerization modification of grafted brush structures because this strategy increases the flexibility with respect to the optimization of the concentration of spiropyran moieties in the brushes. Moreover, the tedious synthesis and purification steps of spiropyran—monomer conjugates are circumvented. 

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