+ Site Statistics
+ Search Articles
+ Subscribe to Site Feeds
Most Shared
PDF Full Text
+ PDF Full Text
Request PDF Full Text
+ Follow Us
Follow on Facebook
Follow on Twitter
Follow on LinkedIn
+ Translate
+ Recently Requested

Radical Nature of Cu-Catalyzed Controlled Radical Polymerizations (Atom Transfer Radical Polymerization)

Radical Nature of Cu-Catalyzed Controlled Radical Polymerizations (Atom Transfer Radical Polymerization)

Macromolecules 31(15): 4710-4717

Copper-catalyzed atom transfer radical polymerization (ATRP) is one of the most robust and precise techniques for controlling radical polymerization. The very good control of molecular weights, polydispersities, functionalities, chain composition, and topologies unusual for radical systems combined with the application of transition metals as catalysts requires more detailed mechanistic studies and proof of the radical nature of active species. The following results are in agreement with the radical nature of ATRP: reverse ATRP, chemoselectivities similar to those for conventional radical polymerization (effect of additives and inhibitors/scavengers, reactivity ratios, transfer coefficients), regioselectivities similar to those for conventional radical polymerization (low proportion of head-to-head units and expected structure of both tail and head end groups), stereoselectivities (tacticities) similar to that in conventional radical polymerization, EPR detection of X-Mtn+1 species resulting from the persistent radical effect, and confirmation of the termination by doubling molecular weights as well as cross-linking with multifunctional initiators and inimers. In addition, it seems that, in most ATRP systems, the contribution of degenerative transfer and reversible formation of organometallic intermediates is small and a halogen atom is transferred in the concerted process rather than in a two-step process with the involvement of radical anions.

(PDF emailed within 0-6 h: $19.90)

Accession: 047160982

Download citation: RISBibTeXText

PMID: 9680403

DOI: 10.1021/ma980357b

Related references

Atom transfer radical polymerization from nanoparticles: a tool for the preparation of well-defined hybrid nanostructures and for understanding the chemistry of controlled/"living" radical polymerizations from surfaces. Journal of the American Chemical Society 123(31): 7497-7505, 2001

Persistent radical effect in action: kinetic studies of copper-catalyzed atom transfer radical addition in the presence of free-radical diazo initiators as reducing agents. Inorganic Chemistry 48(18): 9018-9026, 2009

Degradable copolymers with incorporated ester groups by radical ring-opening polymerization using atom transfer radical polymerization. Polimery 62(4): 262-271, 2017

Uniform PEO star polymers synthesized in water via free radical polymerization or atom transfer radical polymerization. Macromolecular Rapid Communications 32(1): 74-81, 2011

Nanostructured hybrid hydrogels prepared by a combination of atom transfer radical polymerization and free radical polymerization. Biomaterials 30(29): 5270-5278, 2009

Synthesis of block copolymers by combination of atom transfer radical polymerization and visible light-induced free radical promoted cationic polymerization. Macromolecular Rapid Communications 33(4): 309-313, 2013

Integration of CuAAC Polymerization and Controlled Radical Polymerization into Electron Transfer Mediated "Click-Radical" Concurrent Polymerization. Macromolecular Rapid Communications 38(6), 2017

The radical trap in atom transfer radical polymerization need not be thermodynamically stable. A study of the MoX(3)(PMe(3))(3) catalysts. Journal of the American Chemical Society 127(16): 5946-5956, 2005

Palladium-Catalyzed Atom-Transfer Radical Cyclization at Remote Unactivated C(sp 3 )-H Sites: Hydrogen-Atom Transfer of Hybrid Vinyl Palladium Radical Intermediates. Angewandte Chemie 57(10): 2712-2715, 2018

DPPF-Catalyzed Atom-Transfer Radical Cyclization via Allylic Radical. Organic Letters 19(23): 6328-6331, 2017

Atom transfer radical polymerization (ATRP) and organometallic mediated radical polymerization (OMRP) of styrene mediated by diaminobis(phenolato)iron(II) complexes: a DFT study. Inorganic Chemistry 53(14): 7580-7590, 2014

Copper catalyzed atom transfer radical cascade reactions in the presence of free-radical diazo initiators as reducing agents. Chemical Communications 2009(21): 3029-3031, 2009

Phosphorus-containing ligands for iron(III)-catalyzed atom transfer radical polymerization. Angewandte Chemie 47(34): 6426-6429, 2008

An atom transfer radical polymerization system: catalyzed by an iron catalyst in PEG-400. Green Chemistry 17(1): 271-278, 2015

Cascade synthesis of chiral block copolymers combining lipase catalyzed ring opening polymerization and atom transfer radical polymerization. Biomacromolecules 5(5): 1862-1868, 2004