radical polymerization; atom transfer radical polymerization (ATRP)
Abstract :
[en] NiBr2(PPh3)2 has been found to be an efficient catalyst for the ATRP of methyl methacrylate (MMA) and n-butyl acrylate (n-BuA) initiated by an alkyl halide in the absence of any activator (e.g., Lewis acid) at 85 °C. The molecular weight distribution of the poly(meth)acrylates is narrow (Mw/Mn = 1.1−1.4). However, some side reactions (more likely coupling reactions) are observed at high monomer conversions in the case of n-BuA. An excess of PPh3 has proved to increase the polymerization rate of MMA while preserving the control of the molecular parameters. When the catalyst/initiator molar ratio is too small (e.g., 0.05), the polymerization rate decreases, the polydispersity increases, and the initiation is less efficient. α-Acid and α-hydroxyl end groups have been successfully attached to the chains by using functional initiators, such as 2-bromo-2-methylpropionic acid and 2,2‘,2‘ ‘-tribromoethanol. Reactivity ratios for the MMA/n-BuA comonomer pair have been measured and found to be close to the values observed for a conventional free-radical polymerization. Diethyl meso-2,5-dibromoadipate has been used as a difunctional initiator for the n-BuA polymerization, leading to α,ω-bromo-poly(n-BuA) of narrow molecular weight distribution. Finally, the thermal stability of PMMA is consistent with the lack of termination reactions, while Tg is as high as 125 °C.
Research Center/Unit :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Materials science & engineering Chemistry
Author, co-author :
Moineau, Georges; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Minet, Michaël; 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)
Teyssié, Philippe ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Senninger, Thierry; Groupement de Recherches de Lacq, France > Service Polymères de Grande Diffusion et Catalyse
Jérôme, Robert ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Language :
English
Title :
Controlled radical polymerization of (meth)acrylates by ATRP with NiBr2(PPh3)2 as catalyst
Publication date :
12 January 1999
Journal title :
Macromolecules
ISSN :
0024-9297
eISSN :
1520-5835
Publisher :
Amer Chemical Soc, Washington, United States - Washington
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