Photoinitiated alternating copolymerization of vinyl ethers with chlorotrifluoroethylene

Abstract

The photoinitiated copolymerization of chlorotrifluoroethylene (CTFE) with several vinyl ethers [ethyl vinyl ether (EVE), 2‐chloroethyl vinyl ether (CEVE), cyclohexyl vinyl ether (CHVE), 4‐hydroxybutyl vinyl ether (HBVE)] was studied. CTFE is an acceptor monomer (e ∼ 1.5) whereas vinyl ethers are donor monomers (e ∼ −1.5), and therefore their copolymerization led to alternating copolymers, as indicated by elementary analysis. The equilibrium constant (KF) of the charge‐transfer complex formation (CTC) was determined by 19F NMR spectroscopy. Under our experimental conditions, KF was low for CHVE/CTFE and HBVE/CTFE systems, 0.058 and 0.013 l mol−1 respectively. It can be assumed that the copolymerization involves the free monomers rather than propagation via the donor–acceptor complex. The alternating structure arises from the great difference in polarity between the two types of monomers. Several functional copolymers were prepared in good yield and with molecular weight close to 15 000 g mol−1. © 2002 Society of Chemical Industry

Radical copolymerisation of chlorotrifluoroethylene with isobutyl vinyl ether initiated by the persistent perfluoro-3-ethyl-2,4-dimethyl-3-pentyl radical

“…The spectra agree with what is expected for poly(CTFE-altiBuVE) copolymer and demonstrates that the system produced via •CF 3 radical initiation is alternating, as evidenced by the absence of any peaks in the -127 ppm range, indicative of CFCl groups in CTFE-CTFE dyads, in the 19 F NMR spectrum [16][17][18][19] .…”

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New fluorinated polymers bearing pendant phosphonic groups for fuel cell membranes: Part 1 synthesis and characterizations of the fluorinated polymeric backbone

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