Polystyrene ATRP approach

Another approach to incorporate a block structure was to use the multifunctional precursor shown in Fig. 35 and grow blocks from the core of the hyperbranched structure. Such star-like polymers with 80 pnBA blocks were obtained [ 130]. In a similar way, hyperbranched polymers from VBC were used to initiate the ATRP of nBA [130] and St [264]. Dendrigraft polystyrene was found to display a lower intrinsic viscosity and higher thermal stability than linear polystyrenes [264]. 

Beyond these three main concepts, the inverse bioconjugation approach offers another strategy to connect peptides or proteins with synthetic polymers. Using a solid support, which is preloaded with a polymer block, the biological molecule can be assembled in a stepwise fashion through solid-phase synthesis. Mutter and coworkers first showed the attachment of PEO to a poly(styrene) resin via a benzyl ether linker. This concept was finally developed further by Bayer and Rapp leading to a commercially available PAP resin, which is widely applied in solid-phase peptide synthesis. In a similar approach. Lutz, Borner, and coworkers demonstrated the preparation of cleavable and non-cleavable soluble polystyrene supports by ATRP for the liquid-phase synthesis of peptide-polymer conjugates. ... 

Zhang et al. controlled the size of nanoparticles by exploiting the pH and temperature responsiveness ofa poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) brush [68]. Briefly, a PDMAEMA bmsh was synthesized onto a polystyrene latex nanoparticle via atom transfer radical polymerization (ATRP). Dynamic light-scattering events indicated that pH changes led to temperature changes in solution, which resulted in an alteration in particle size. This approach could be useful in enzyme immobilization or protein separation. 

Reversible addition-fragmentation chain transfer polymerization (RAFT) polymerization of methyl acrylate was combined with cationic polymerization of THF to synthesize comb copolymers. Asymmetric star block copolymers based on polystyrene (PS), PTHF, and PMMA were synthesized by a combination of CROP and redox polymerization methods. Miktoarm star polymers containing poly(THF) and polystyrene arms were also obtained by combining CROP and ATRP methods. Another approach for the synthesis of block copolymers... 

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