Issue 3, 2015

Controlled copolymerization of n-butyl acrylate with semifluorinated acrylates by RAFT polymerization

Abstract

By reversible addition fragmentation chain transfer (RAFT) copolymerization of n-butyl acrylate (nBuA) with semifluorinated acrylates, such as 2,2,2-trifluoroethyl acrylate (TFEA), 2,2,3,3,3-pentafluoropropyl acrylate (PFPA) and 2,2,3,3,4,4,4-heptafluorobutyl acrylate (HFBA), up to 90.2% co-monomer conversion was accomplished. When using dibenzyl trithiocarbonate (DBTTC) as a chain transfer agent (CTA) in DMF at 65 °C, excellent control of molecular weight (Mn) together with a low molecular weight distribution (PDI) was achieved. The successful synthesis of well-controlled semifluorinated copolymers was checked by a combination of 1H NMR, 19F NMR, SEC and ESI-TOF mass spectrometry, proving their composition via1H NMR and ESI-TOF mass spectrometry. The reactivity ratios (r) of each pair of co-monomers were assessed using Fineman–Ross (FR) and Kelen–Tüdos (KT) laws: in all cases, the product (rM1 × rM2) was close to unity, indicating a random distribution of each pair of co-monomers along the semifluorinated copolymer backbone. Results were further confirmed by applying the Qe scheme.

Graphical abstract: Controlled copolymerization of n-butyl acrylate with semifluorinated acrylates by RAFT polymerization

Supplementary files

Article information

Article type
Paper
Submitted
08 Aug 2014
Accepted
15 Sep 2014
First published
16 Sep 2014

Polym. Chem., 2015,6, 448-458

Author version available

Controlled copolymerization of n-butyl acrylate with semifluorinated acrylates by RAFT polymerization

S. Chen and W. H. Binder, Polym. Chem., 2015, 6, 448 DOI: 10.1039/C4PY01084A

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