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. 2021 Mar 29;7(2):36. doi: 10.3390/gels7020036

Table 1.

Controlled/living radical polymerization (CLRP) techniques used in polymerization and NG design.

CLRP Method Main Features References
NMP
  • Suitable for surfactant-free nanoscaffold formation in aqueous dispersion.

  • Reversible termination mechanism between the growing-propagating radicals and the nitroxide, which acts as a control agent.

  • Well-defined structures of the polymeric backbone with the opportunity to add functional moieties before NG formation.

[54,55,56]
ATRP
  • Fast dynamic equilibrium between radicals and dormant alkyl halides.

  • Catalytic process to activate the dormant alkyl halide, generating a complex with higher oxidation state and a macro-radical ‘living’ polymer. The latter can propagate or is deactivated back to ‘dormant’ polymer, preventing bimolecular termination.

  • Variations vs the traditional use of metal catalysts: activation by electron transfer (ARGET-ATRP), electrochemically mediated transfer (eATRP), zerovalent metals in supplemental activators and reducing agents (SARA-ATRP), initiators for continuous activator regeneration (ICAR-ATRP), photochemical reduction (photoATRP), and metal-free ATRP.

[42,57,58,59,60]
RAFT
  • Metal-free polymerization chemistry.

  • Use of fast reversible transfer of chain transfer agents (CTA, typically a thio-carbonyl-thio group) to control the propagation of radicals and the formation of dormant species. It ensures a prolonged lifetime of growing chains.

  • Minimal to null undesirable background polymerization.

[61,62,63,64,65]
RITP
  • Reversible deactivation of radicals mediated by iodine.

  • Synthesis of well-defined polymers with programmable compositions and architectures, narrow molecular weight distributions.

  • Simple reaction system, various types of monomers, mild reaction conditions and tolerance to the reactant purity.

[66,67]
MADIX
  • The use of the xanthate promotes the design of NGs with high-density of crosslinking points and polymer chains without formation of macrostructures.

  • Possibility of generating core-shell star nanosystems by chain extension from branched polymeric precursors.

  • It can be applied in combination with RAFT.

[53,68,69]