Atom Transfer Radical Polymerization (ATRP) and Reversible Addition-Fragmentation Chain-Transfer (RAFT) Polymerization

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Atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain-transfer (RAFT) polymerization are the two most prevalent controlled radical polymerization (CRP) methods.¹⁾ Because of their ability to control resultant polymers and their wide monomers and solvents scope, ATRP and RAFT polymerization have extended material development possibility of materials scientists and life scientists. For instance, these polymerization methods enable scientists to synthesize specialized structure polymers including star shaped or hyper branched polymers, and grafted polymers from various substrates or nanoparticles. Therefore ATRP and RAFT polymerization techniques are used in research and industrial applications like lubricants and medical applications such as bioconjugates and drug delivery systems (DDS).^2,3)

Comparison between ATRP and RAFT polymerization

ATRP and RAFT polymerization techniques are both capable to synthesize polymers with controlled average molecular weights, molecular weight distributions, and structures. In addition to that, they are beneficial to polymerize acrylic monomers and styrene monomers which are easy to synthesize functional monomers and applicable to conventional free radical polymerization.

	ATRP	RAFT Polymerization
Reagents	ATRP initiators Ligands Transition metal catalysts	RAFT agents (chain-transfer agent，CTA) Radical initiators
End groups
End groups removal	Mainly for improving stability of resultant polymers nBu₃SnH,⁴⁾ Pd/C and H₂,⁵⁾ 10-Phenylphenothiazine and lights,⁶⁾ etc. are used.	Mainly for removing color and odor of resultant polymers Radical induced reduction, radical addition-fragmentation-coupling, thermolysis, photo-reduction using 10-Phenylphenothiazine, etc.^6,7,8)
End groups functionalization	Ref. 9, 10 e. g.)	Ref. 7, 8 e. g.)
Polymerization in aqueous media	Challenging	Applicable
Acidic monomers	Unfavorable	Applicable
pH	Not applicable in low-pH because of protonation of ligands	Not applicable in high-pH because of degradation of RAFT agents
Oxygen tolerance	Although conventional method has no oxygen tolerance, several oxygen tolerant ATRPs have been reported.¹¹⁾	PET-RAFT polymerization is known as oxygen tolerance method.¹²⁾
Other advantage	Generally coloring is not problematic without end group removal/fuctionalization.	Because RAFT is performed just adding RAFT agent to free radical polymerization system, existing facilities for free radical polymerization might be applied.

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Common ATRP initiators, ATRP ligands, RAFT agents appropriate to each monomers

The table below shows representative ATRP and RAFT reagents used to polymerize acrylates, acrylamides, methacrylates, and methacrylamides, which are frequently used by materials scientists and life scientists.
Careful selection of initiator and ligand for ATRP, and careful selection of RAFT agent according to monomer structures are required for achieving sufficient control.