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Multifunctional Poly(vinyl ethers) by Controlled Cationic Polymerisation in a Fluorinated Solvent
Author(s) -
Castelvetro Valter,
Bontà Pittaluga Gianluca,
Ciardelli Francesco
Publication year - 2001
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/1521-3935(20010601)202:10<2093::aid-macp2093>3.0.co;2-b
Subject(s) - living cationic polymerization , vinyl ether , cationic polymerization , polymer chemistry , copolymer , polymerization , chemistry , monomer , solvent , ether , vinyl acetate , living polymerization , organic chemistry , radical polymerization , polymer
The living nature of the cationic polymerisation of butyl vinyl ether (BVE) in the fluorinated solvent 1,1,2‐trichloro trifluoroethane was studied, using the initiating system composed of ethyl aluminium dichloride (EtAlCl 2 ) as the activator and 1‐butoxyethyl acetate (BEA) as the initiator. BVE homopolymerises in a seemingly living fashion at T ≤ 0°C in the presence of 1,4‐dioxane (DO) as a stabilising Lewis base, although the fluorinated solvent slows down the polymerisation appreciably. Less than quantitative reinitiation has been observed when a second BVE feed was added to the living macrocation at nearly quantitative monomer conversion. The functional monomers 2‐chloroethyl vinyl ether (CLEVE), 3‐cyano‐3‐ethoxycarbonylpropyl vinyl ether (CNEVE) and 1H,1H,2H,2H ‐perfluorodecyl vinyl ether (XFDVE) were submitted to polymerisation under the same conditions that allow to achieve a quasi‐living BVE polymerisation. CLEVE gave a homopolymer with relatively narrow molecular‐weight distribution (MWD), while efficient polymerisation of XFDVE was only achieved with BF 3 etherate as the initiator. Copolymerisation of the various functional vinyl ethers with BVE takes place in a more controlled fashion, yielding products with narrow MWD index ( M w / M w = 1.2–1.35), at moderate functional vinyl ether conversions. Block copolymers could be synthesised from poly(BVE) living macrocations; these are probably characterised by a hybrid structure, consisting of a pure BVE block and a second block of BVE‐functional vinyl ether copolymer.