Atom-Transfer Radical-Polymerization (ATRP)

Reaction [1]:

Mechanism [2]:

Specific example [3]:

Highlights and Significance:

  1. ATRP is a controlled radical process for polymerization of styrenic, acrylic, and methacrylic monomers. [4]
  2. The radical termination reaction is not fast because the concentration of active radicals is low. [5]
  3. External visible light stimulation ATRP has a high responding speed and excellent functional group tolerance. [6]


1.     Wei, Q., Emerging approaches to the surface modification of textiles. In Surface Modification of Textiles, Elsevier: 2009; pp 318-323.

2.     Wang, J.-S.; Matyjaszewski, K., Controlled/” living” radical polymerization. atom transfer radical polymerization in the presence of transition-metal complexes. J. Am. Chem. Soc. 1995, 117 (20), 5614-5615.

3.     Zaborniak, I.; Chmielarz, P.; Matyjaszewski, K., Modification of wood-based materials by atom transfer radical polymerization methods. Eur. Polym. J. 2019, 109253.

4.     Moineau, C.; Minet, M.; Teyssié, P.; Jérôme, R., Synthesis and Characterization of Poly (methyl methacrylate)-block-poly (n-butyl acrylate)-block-poly (methyl methacrylate) Copolymers by Two-Step Controlled Radical Polymerization (ATRP) Catalyzed by NiBr2 (PPh3) 2, 1. Macromolecules 1999, 32 (25), 8277-8282.

5.     Fantin, M.; Isse, A. A.; Venzo, A.; Gennaro, A.; Matyjaszewski, K., Atom transfer radical polymerization of methacrylic acid: a won challenge. J. Am. Chem. Soc. 2016, 138 (23), 7216-7219.

6.     Fors, B. P.; Hawker, C. J., Control of a living radical polymerization of methacrylates by light. Angew. Chem. 2012, 51 (35), 8850-8853.