Atom transfer radical polymerization by [RuCl2(PPh3)2(amine)] catalysts: Cyclic amines as tuner of reactivity

Atom transfer radical polymerizations (ATRP) of styrene (St) and methyl methacrylate (MMA) mediated by [RuCl 2 (PPh 3 ) 2 (amine)] complexes, with amine = pyrrolidine ( 1 ), piperidine ( 2 ), or perhydroazepine ( 3 ), were investigated as a function of time, temperature, and concentrations of monome...

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Bibliographic Details
Published in:Journal of polymer research 2017-10, Vol.24 (11), p.1, Article 196
Main Authors: Cruz, Thais R., Borim, Patrícia, Goi, Beatriz E., Silva Sá, José L., Lima-Neto, Benedito S., Carvalho, Valdemiro P.
Format: Article
Language:English
Subjects:
Amines
Characterization and Evaluation of Materials
Chemistry
Chemistry and Materials Science
Industrial Chemistry/Chemical Engineering
Monomers
NMR
Nuclear magnetic resonance
Original Paper
Piperidine
Polymer Sciences
Polymerization
Polymethyl methacrylate
Steric hindrance
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Summary:Atom transfer radical polymerizations (ATRP) of styrene (St) and methyl methacrylate (MMA) mediated by [RuCl 2 (PPh 3 ) 2 (amine)] complexes, with amine = pyrrolidine ( 1 ), piperidine ( 2 ), or perhydroazepine ( 3 ), were investigated as a function of time, temperature, and concentrations of monomers and 2-bromoisobutyrate as initiator. The plots of ln([M] 0 /[M]) vs. time and molecular weights vs. monomer conversion were linear and the dispersity indexes decreased with increasing monomer conversions. The complexes 1 , 2 , and 3 were able to mediate the polymerizations with acceptable rate and level of control. Differences in the rate and control of polymerization were observed in the order 3  >  2  >  1 for both monomers. The activities were discussed considering the steric hindrance and electronic characteristics of the amines as ancillary ligands in the metal centres, considering studies by cyclic voltammetry and NMR.
ISSN:1022-9760
1572-8935
DOI:10.1007/s10965-017-1354-9