Addressing the role of triphenylphosphine in copper catalyzed ATRP. Issue 44 (22nd October 2018)

• Record Type: Journal Article
• Authors: Costa, João R. C.; Góis, Joana R.; De Bon, Francesco; Serra, Arménio C.; Guliashvili, Tamaz; Isse, Abdirisak A.; Gennaro, Armando; Coelho, Jorge F. J.
• Is Part Of: Polymer chemistry. Volume 9:Issue 44(2018)
• Page Start: 5348
• Page End: 5358
• Publication Date: 2018-10-22
• Subjects: Polymers -- Periodicals; Macromolecules -- Periodicals; Polymerization -- Periodicals; 547.705
• DOI: 10.1039/c8py01245h
• Languages: English
• ISSNs: 1759-9954

Abstract

Abstract : A new Atom Transfer Radical Polymerization (ATRP) process with triphenylphosphine (PPh3 ) and [Cu II Me6 TREN] 2+ as the catalyst system is reported. Abstract : A new Atom Transfer Radical Polymerization (ATRP) process with triphenylphosphine (PPh3 ) and [Cu II Me6 TREN] 2+ as the catalyst system is reported. It is shown that PPh3 can act not only as an efficient reducing agent (RA) but also as a supplemental activator (SA). The kinetics and mechanism of SARA ATRP of methyl acrylate (MA) in DMSO and DMSO/H2 O (90/10 v/v) were investigated in detail. The polymers presented controlled molecular weight, very low dispersity ( Đ ≈ 1.03), and well-defined chain-end functionality. UV-Vis and electrochemical studies were performed to understand the role of PPh3 and the Cu II Br2 /Me6 TREN complex in MA polymerization. It is demonstrated that the presence of PPh3 does not affect the stability of the [BrCu II Me6 TREN] + deactivator. The reported results reveal the high versatility of PPh3 in ATRP, which, besides being commonly used in iron-mediated polymerizations, can also be employed as a SARA agent in copper-based ATRP systems.