Reversible addition-fragmentation chain transfer methacrylate polymerization

Fijten MWM, Meier MAR, Hoogenboom R, Schubert US (2004) Automated parallel inves-tigations/optimizations of the reversible addition-fragmentation chain transfer polymerization of methyl methacrylate. J Polym Sci Part A Polym Chem 42 5775-5783... 

Segmented terpolymers of poly(alkyl methacrylate)-g-poly(D-lactide)/poly(dimethylsiloxane) (PLA/PDMS) were prepared by combination of a grafting through technique (macromonomer method) and controlled/living radical polymerization such as atom transfer radical polymerization (ATRP) or reversible addition-fragmentation chain transfer polymerization. In a single-step approach, the low molecular weight methacrylate monomer (methyl methacrylate... 

FIGURE 10.2 MALDI TOP mass spectra obtained from the automated spotting of the synthesized poly(methyl methacrylate) polymers at different reaction times. The insert (right top) shows the peak molecular weight (M ) (obtained from MALDI TOFMS spectra) as function of the reaction time. Matrix DCTB. This material is reproduced with permission of John Wiley Sons, Inc. from Fijten MWM, Meier MAR, Hoogenboom R, Schubert US. Automated parallel investigations/optimizations of the reversible addition-fragmentation chain transfer polymerization of methyl methacrylate. J Polym Sci A Polym Chem 2004 42 5775-5783. 

Barner-Kowollik C, Quinn FJ, Nguyen TLU, Heuts JPA, Davis TP. Kinetic investigations of reversible addition fragmentation chain transfer polymerizations cumyl phenyldithioacetate mediated homopolymerizations of styrene and methyl methacrylate. Macromolecules 2001 34 7849-7857. 

You, Y.-Z., Zhou, Q.-H., Manickam, D.S., Wan, L., Mao, G.-Z., and Oupicky, D. (2007) Dually responsive multiblock copolymers via reversible addition-fragmentation chain transfer polymerization synthesis of temperature- and redox-responsive copolymers of poly(N-isopropylacrylamide) and poly(2-(dimethylamino)ethyl methacrylate). Macromokcuks, 40, 8617-8624. 

Photo-induced polymerization of hydroxypropyl-P-CD/methyl methacrylate complex, i.e. HP-P-CD/MMA was performed in aqueous solution, at room temperature with Irgacure 2959, i.e. 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone serving as a photoinitiator [75]. The atom transfer radical polymerization (ATRP) and reversible addition fragmentation chain transfer (RAFT) [76] methods are also used to perform polymerization of the CD/guest monomer complexes in aqueous solutions. 

Chong YK, Moad G, Rizzardo E, Skidmore MA, Thang SH. Reversible addition fragmentation chain transfer polymerization of methyl methacrylate in the presence of Lewis acids an approach to stereocontroUed hving radical polymerization. Macromolecules. 2007 40 9262-9271. 

Enzymatic ROP has also been successfully combined with chemically catalyzed polymerization methods in SCCO2, allowing the formation of block structures. For example, Howdle and coworkers reported a simultaneous use of Novozym 435 with metalblock copolymers of PCL and PMMA [107, 108], whilst a two-step methodology was used to form block copolymers of PCL with poly(fluoro-octyl methacrylates) (PFOMA) [109]. Similar reactions, simultaneously combining reversible addition-fragmentation chain transfer (RAFT) with enzymatic ROP to form block copolymers of polystyrene and PCL, have also been performed in SCCO2 [110]. Block copolymer synthesis in SCCO2 has recently been reviewed [111]. 

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