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Synthesis of well-defined poly(alkyl methacrylate)-graft-polylactone by sequential living polymerization
Mecerreyes, David; Dubois, Philippe; Jérôme, Robert et al.
1999In Macromolecular Chemistry and Physics, 200 (1), p. 156-165
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Keywords :
anionic polymerization; ring-opening polymerization (ROP); lactone; graft polymer
Abstract :
[en] A novel combination of living polymerization reactions has been proposed for the controlled synthesis of poly(alkyl methacrylate)-graft-polylactones. This strategy relies upon the sequential living polymerization of alkyl methacrylates and aliphatic lactones, with an intermediate chemical transformation for shifting from the first mechanism to the second one. In the first step, an alkyl methacrylate (methyl and butyl) is copolymerized with 2-trimethylsiloxyethyl methacrylate (TMSEMA). This living anionic polymerization is initiated with diphenylhexyllithium( DPHLi) in the presence of a μ-ligand, lithium chloride, in THF at - 78 °C. The trimethylsiloxy groups are then hydrolyzed with release of hydroxyl groups which are reacted with triethylaluminum in order to form a multifunctional macroinitiator of the Al alkoxide type. The second step consists of the ring opening polymerization (ROP) of aliphatic lactones (ε-caprolactone, J-valerolactone and 1,4,8-trioxaspiro[4.6]-9-undecanone (TOSUO)) with the formation of novel graft copolymers. As a result of the livingness of both the anionic and the ROP polymerization steps, the molecular weight of both the main backbone and the grafts is predictable, the apparent polydispersity is narrow ( from 1.05 to 1.30) and the grafting density can be controlled being dependent on the distribution of the hydroxyl groups within the precursor backbone.
Research center :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Chemistry
Materials science & engineering
Author, co-author :
Mecerreyes, David;  Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Dubois, 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)
Hedrick, James L;  IBM Almaden Research Center, San Jose, USA
Language :
English
Title :
Synthesis of well-defined poly(alkyl methacrylate)-graft-polylactone by sequential living polymerization
Publication date :
January 1999
Journal title :
Macromolecular Chemistry and Physics
ISSN :
1022-1352
eISSN :
1521-3935
Publisher :
Wiley-V C H Verlag Gmbh, Weinheim, Germany
Volume :
200
Issue :
1
Pages :
156-165
Peer reviewed :
Peer Reviewed verified by ORBi
Funders :
The "Govierno Vasco"
IBM Belgium
BELSPO - SPP Politique scientifique - Service Public Fédéral de Programmation Politique scientifique
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since 18 June 2009

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