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Endgroup‐functionalized polytetrahydrofurans by polymerization with functional triflate esters, 1. PolyTHF‐macromonomers
Author(s) -
Dubreuil Marjorie F.,
Goethals Eric J.
Publication year - 1997
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/macp.1997.021981008
Subject(s) - polymer chemistry , trifluoromethanesulfonate , polymerization , chemistry , copolymer , polymer science , organic chemistry , polymer , catalysis
Abstract Functional esters of trifluoromethanesulfonic acid (triflate esters) have been synthesized by reaction of functional alcohols (allyl alcohol, 2‐hydroxyethyl acrylate (HEA) and methacrylate (HEMA), 4‐hydroxybutyl acrylate (HBA)) with triflic anhydride in the presence of 2,6‐di‐ tert ‐butylpyridine. These esters were used in situ as initiators for the polymerization of tetrahydrofuran (THF), with the purpose to synthesize endgroup‐functionalized polyTHF's. The method was first tested with the system butanol/triflic anhydride. With this combination, quantitative formation of the ester and, subsequently, controlled polymerization of THF was realized. Similar results were obtained with the system allyl alcohol/triflic anhydride. With 2‐hydroxyethyl acrylate (HEA) and 2‐hydroxyethyl methacrylate (HEMA), the synthesis of the triflate ester was accompanied by the formation of substantial amounts of ether formed by reaction of the triflate ester with a second molecule of alcohol. This was attributed to an enhanced reactivity of the triflate ester due to nucleophilic assistance by the carbonyl group in γ‐position. This assistance is not possible with 4‐hydroxybutyl acrylate (HBA) and with this alcohol, the formation of the ester was almost quantitative. The synthesis of polyTHF acrylate macromonomer was successful with the latter system.