The Preparation and Chemistry of Dicationically Active Polymers of Tetrahydrofuran
- 1 November 1973
- journal article
- research article
- Published by Taylor & Francis in Journal of Macromolecular Science: Part A - Chemistry
- Vol. 7 (7), 1399-1413
- https://doi.org/10.1080/10601327308060509
Abstract
The anhydrides of the very strong acids, CF 3 SO 3 H and FSO 3 H, polymerize tetrahydrofuran (THF) to give a living polyether having cationic activity at each chain end. The surprising fact that both chain ends are cationically active necessitates the postulation of a reaction mechanism wherein the YSO,-ester end group (Y=CF 3 or F) formed as an intermediate in the polymerization generates an oxonium ion by a subsequent O-alkylation reaction involving either a THF molecule or a nearest neighbor ether group of the polymer chain. Kinetic studies of polymerizations involving (CF, SO,) 2 0 and the bis-ester, CF 3 SO 3 —C 4 H 5 —O 3 SCF 3 , as initiators indicate that chain growth is much faster where an oxonium ion rather than an ester is the end group. The chemistry of poly-THF dications is discussed. These are strong alkylating agents which make possible the facile preparation of unusual copolymers, block copolymers, and functionally terminated polymers.Keywords
This publication has 10 references indexed in Scilit:
- Reactions of pyrosulfuryl fluorideThe Journal of Organic Chemistry, 1971
- Block Copolymerization. II. Polymerization of Tetrahydrofuran by Bifunctional Cationic InitiatorPolymer Journal, 1971
- Solvolysis reactivities of ethyl and n-propyl trifluoromethanesulfonates in trifluoroethanol and trifluoroacetic acid.Tetrahedron Letters, 1970
- Vinyl cations in solvolysis reactionsAccounts of Chemical Research, 1970
- Controlled Block Copolymerization of Tetrahydrofuran and New Aspects of Tetrahydrofuran Polymerization KineticsPublished by Springer Nature ,1970
- Polymerization of tetrahydrofuran: A radiochemical study of the initiation mechanismJournal of Polymer Science Part A-1: Polymer Chemistry, 1969
- The Reaction of Trityl Salts with 2-Methyltetrahydrofuran and with TetrahydrofuranMacromolecules, 1968
- PolytetrahydrofuranAdvances in Polymer Science, 1967
- The initiation process in the polymerization of tetrahydrofuran with carbonium ion saltsJournal of Polymer Science Part A-1: Polymer Chemistry, 1967
- Perfluoroalkanesulfonate Esters as Alkylating AgentsThe Journal of Organic Chemistry, 1965