Reversible addition fragmentation termination copolymers

The bifunctional initiator approach using reversible addition fragmentation chain-transfer polymerization (RAFT) as the free-radical controlling mechanism was soon to follow and block copolymers of styrene and caprolactone ensued [58]. In this case, a trithiocarbonate species having a terminal primary hydroxyl group provided the dual initiation (Figure 13.3). The resultant polymer was terminated with a trithiocarbonate reduction of the trithiocarbonate to a thiol allows synthesis of a-hydroxyl-co-thiol polymers which are of particular interest in biopolymer applications. 

Due to the relative ease of control, temperature is one of the most widely used external stimuli for the synthesis of stimulus-responsive bmshes. In this case, thermoresponsive polymer bmshes from poly(N-isopropylacrylamide) (PNIPAM) are the most intensively studied responsive bmshes that display a lower critical solution temperature (LOST) in a suitable solvent. Below the critical point, the polymer chains interact preferentially with the solvent and adopt a swollen, extended conformation. Above the critical point, the polymer chains collapse as they become more solvophobic. Jayachandran et reported the synthesis of PNIPAM homopolymer and block copolymer brushes on the surface of latex particles by aqueous ATRP. Urey demonstrated that PNIPAM brushes were sensitive to temperature and salt concentration. Zhu et synthesized Au-NPs stabilized with thiol-terminated PNIPAM via the grafting to approach. These thermosensitive Au-NPs exhibit a sharp, reversible, dear opaque transition in solution between 25 and 30 °C. Shan et al. prepared PNIPAM-coated Au-NPs using both grafting to and graft from approaches. Lv et al. prepared dual-sensitive polymer by reversible addition-fragmentation chain transfer (RAFT) polymerization of N-isopropylacrylamide from trithiocarbonate groups linked to dextran and sucdnoylation of dextran after polymerization. Such dextran-based dual-sensitive polymer is employed to endow Au-NPs with stability and pH and temperature sensitivity. 

A block copolymer of poly(A-isopropylacrylamide) (PNI-PAAm) and PLA may combine the thermosensitive property of PNIPAAm and the biodegradable property of PLA. Polymeric micelles from such polymers can improve protein release properties. Temperature change can alter the hydro-philicity and conformation of PNIPAAm, which may affect the physicochemical properties of microspheres of the polymer. Amphiphilic block copolymers of P(NIPAAm-Z -LA) have been prepared by ROP of LA in toluene using Sn(Oct)2 as a catalyst and hydroxyl-terminated PNIPAAm, as depicted in Figure 4.6 [62]. Such copolymers have recently been synthesized by ROP of lactide using the two hydroxyl groups of 5, 5 -bis(2-hydroxyethyl-2 -butyrate)trithiocarbonate (BHBT). PLA-Z -PNIPAAm-Z -PLA was prepared by reversible addition-fragmentation chain transfer (RAFT) polymer-... 

The development of the CRP based on the idea of reversible chain termination decrease the disadvantage of the free-radical polymerization and permits the synthesis of defined block copolymer structures. The growing demand for well-defined and ftinctional soft materials in nanoscale applications has led to a dramatic increase in the development of procedures that combine architectural control with flexibility in the incorporation of ftinctional groups. Thus, there is a strong increase in the elucidation of a variety of controlled polymerization strat es in the past years. " These include nitroxide-mediated radical polymerization (NMRP), atom transfer radical polymerization (ATRP), " and reversible addition-fragmentation chain transfer (RAFT) procedures. Such techniques led to well-defined homo and block copolymers of different architectures whose behavior was investigated in solution and on surfaces. ... 

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