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From the N‐Heterocyclic Carbene‐Catalyzed Conjugate Addition of Alcohols to the Controlled Polymerization of (Meth)acrylates
Author(s) -
Ottou Winnie Nzahou,
Bourichon Damien,
Vignolle Joan,
Wirotius AnneLaure,
Robert Fredéric,
Landais Yannick,
Sotiropoulos JeanMarc,
Miqueu Karinne,
Taton Daniel
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201500594
Subject(s) - polymer chemistry , acrylate , chemistry , methyl methacrylate , monomer , polymerization , copolymer , catalysis , methyl acrylate , alkoxy group , organic chemistry , polymer , alkyl
Among various N‐heterocyclic carbenes (NHCs) tested, only 1,3‐bis( tert ‐butyl)imidazol‐2‐ylidene (NHC t Bu ) 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 t Bu .