Tandem catalysis of Atom Transfer Radical Polymerization of acrylonitrile based on simultaneous use of two copper complexes

• Published in: Journal of polymer research Vol. 28; no. 12
• Main Authors: Stakhi, Sergey A., Grishin, Dmitry F., Grishin, Ivan D.
• Format: Journal Article
• Language: English
• Published: Dordrecht Springer Netherlands 01-12-2021; Springer Nature B.V
• Subjects: Catalysis; Characterization and Evaluation of Materials; Chemistry; Chemistry and Materials Science; Coordination compounds; Copolymers; Copper compounds; Dimethylitaconate; Industrial Chemistry/Chemical Engineering; Molecular weight; Original Paper; Polymer Sciences; Polymerization; Cyclic voltammetry; RDPR; Acrylonitrile; Tandem catalysis; ARGET ATRP; Copper complexes
• ISSN: 1022-9760; 1572-8935
• DOI: 10.1007/s10965-021-02821-6

The novel approach for conducting ARGET ATRP based on simultaneous use of two copper complexes based on tris[2-(dimethylamino)ethyl]amine (Me
6
TREN), 2,2’-bipyridine (bipy) and tris(2-pyridylmethyl)amine (TPMA) in one pot is proposed. This approach allows to increase the rate of polymerization of acrylonitrile and to achieve polymers with high molecular weights. The performed electrochemical studies allowed establishing the possible mechanism of tandem catalysis where the more reducing complex mostly acts as activator determining the high polymerization rate while the second one reversible deactivates polymer chain preserving the control over the process. The influence of initiator nature and the ratio between copper catalysts on the polymerization rate and the molecular weight parameters of the samples was studied. It was shown that the proposed system may be applied for obtaining well-defined copolymers of acrylonitrile with methyl acrylate and dimethyl itaconate via ARGET ATRP mechanism using low copper concentrations.