Cooperative Hydrogen-Bond Pairing in Organocatalytic Ring-Opening Polymerization

Cooperative Hydrogen-Bond Pairing in Organocatalytic Ring-Opening Polymerization

Thiourea (TU)/amine base cocatalysts are commonly employed for well-controlled, highly active “living” organocatalytic ring-opening polymerizations (ROPs) of cyclic esters and carbonates. In this work, several of the most active cocatalyst pairs are shown by 1H NMR binding studies to be highly assoc...

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Bibliographic Details
Published in:Macromolecules Vol. 47; no. 21; pp. 7463 - 7468
Main Authors: Kazakov, Oleg I, Datta, Partha P, Isajani, Meghedi, Kiesewetter, Elizabeth T, Kiesewetter, Matthew K
Format: Journal Article
Language:English
Published: Washington, DC American Chemical Society 11-11-2014
Subjects:
Applied sciences
Exact sciences and technology
Organic polymers
Physicochemistry of polymers
Polymerization
Preparation, kinetics, thermodynamics, mechanism and catalysts
1,8-Diazabicyclo[5.4.0]undec-7-ene
Ring opening polymerization
Catalytic reaction
Angular nitrogen heterocycle
Living polymer
Benzyl alcohol
Experimental study
Lactone polymer
Solution polymerization
Aliphatic polymer
Reaction mechanism
Thiourea
Catalyst activity
Polycaprolactone
Polycarbonate
Hydrogen bond
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Summary:Thiourea (TU)/amine base cocatalysts are commonly employed for well-controlled, highly active “living” organocatalytic ring-opening polymerizations (ROPs) of cyclic esters and carbonates. In this work, several of the most active cocatalyst pairs are shown by 1H NMR binding studies to be highly associated in solution, dominating all other known noncovalent catalyst/reagent interactions during ROP. One strongly binding catalyst pair behaves kinetically as a unimolecular catalyst species. The high selectivity and activity exhibited by these ROP organocatalysts are attributed to the strong binding between the two cocatalysts, and the predictive utility of these binding parameters is applied for the discovery of a new, highly active cocatalyst pair.
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ISSN:0024-9297
1520-5835
DOI:10.1021/ma501847x