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Anionic polymerization of methacrylate monomers initiated by lithium dialkylamides
Antoun, Sayed; Teyssié, Philippe; Jérôme, Robert
1997In Journal of Polymer Science. Part A, Polymer Chemistry, 35 (17), p. 3637-3544
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Keywords :
anionic polymerization; (meth)acrylate
Abstract :
[en] The anionic polymerization of methacrylate monomers has been investigated with lithium dialkylamides as initiators in THF and toluene, respectively. Theoretical arguments and previous studies of mixed aggregates of lithiated organic compounds support the complexity of these systems. Lithium diisopropylamide (LDA) shows the highest initiation efficiency (e.g., f = 75% in THF at -78°C). Interestingly enough, lithium chloride has a remarkable beneficial effect on the methacrylates polymerization in THF at -78°C, due to the formation of 1 : 1 mixed dimer with LDA, which promotes a well-controlled anionic polymerization (Mw/Mn = 1.05) with a high initiation efficiency (94%). The less bulky lithium-diethylamide (LDEA) is much less efficient (f = 26%), essentially as a result of some associated dormant species and side reactions on the carbonyl group of MMA. Although various types of ligands have been screened, no remarkable improvement of LDEA efficiency has been observed. Lithium bis(trimethylsilyl)amide (LTMSA) has also been used to increase the steric hindrance of the initiator. This compound is, however, unable to initiate the methacrylates polymerization, more likely because of a too low basicity and a too strong Li - N bond. © 1997 John Wiley
Research center :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Chemistry
Materials science & engineering
Author, co-author :
Antoun, Sayed;  Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Teyssié, Philippe ;  Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Jérôme, Robert ;  Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Language :
English
Title :
Anionic polymerization of methacrylate monomers initiated by lithium dialkylamides
Publication date :
December 1997
Journal title :
Journal of Polymer Science. Part A, Polymer Chemistry
ISSN :
0887-624X
eISSN :
1099-0518
Publisher :
John Wiley & Sons, Hoboken, United States - New Jersey
Volume :
35
Issue :
17
Pages :
3637-3544
Peer reviewed :
Peer Reviewed verified by ORBi
Funders :
BELSPO - SPP Politique scientifique - Service Public Fédéral de Programmation Politique scientifique
Available on ORBi :
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