From the N-Heterocyclic Carbene-Catalyzed Conjugate Addition of Alcohols to the Controlled Polymerization of (Meth)acrylates | Health & Environmental Research Online (HERO)

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Citation
Tags

HERO ID

3021348

Reference Type

Journal Article

Title

From the N-Heterocyclic Carbene-Catalyzed Conjugate Addition of Alcohols to the Controlled Polymerization of (Meth)acrylates

Author(s)

Ottou, WN; Bourichon, D; Vignolle, J; Wirotius, AL; Robert, F; Landais, Y; Sotiropoulos, JM; Miqueu, K; Taton, D

Year

2015

Is Peer Reviewed?

Yes

Journal

Chemistry: A European Journal
ISSN: 0947-6539
EISSN: 1521-3765

Volume

Issue

Page Numbers

9447-9453

Language

English

PMID

26013759

DOI

10.1002/chem.201500594

Web of Science Id

WOS:000356795000023

Abstract

Among various N-heterocyclic carbenes (NHCs) tested, only 1,3-bis(tert-butyl)imidazol-2-ylidene (NHC(tBu) ) proved to selectively promote the catalytic conjugate addition of alcohols onto (meth)acrylate substrates. This rather rare example of NHC-catalyzed 1,4-addition of alcohols was investigated as a simple means to trigger the polymerization of both methyl methacrylate and methyl acrylate (MMA and MA, respectively). Well-defined α-alkoxy poly(methyl (meth)acrylate) (PM(M)A) chains, the molar masses of which could be controlled by the initial [(meth)acrylate]0/[ROH]0 molar ratio, were ultimately obtained in N,N-dimethylformamide at 25 °C. A hydroxyl-terminated poly(ethylene oxide) (PEO-OH) macro-initiator was also employed to directly access PEO-b-PMMA amphiphilic block copolymers. Investigations into the reaction mechanism by DFT calculations revealed the occurrence of two competitive concerted pathways, involving either the activation of the alcohol or that of the monomer by NHC(tBu) .

Keywords

density functional calculations; N-heterocyclic carbenes; organocatalysis; polymerization; reaction mechanisms