Catalyzed chain growth of polyethylene on magnesium for the synthesis of macroalkoxyamines: Application to the production of block copolymers using controlled radical polymerization |
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Authors: | Ricardo Godoy Lopez Christophe Boisson Franck D'Agosto Roger Spitz Fernande Boisson Didier Gigmes Denis Bertin |
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Institution: | 1. Laboratoire de Chimie et Procédés de Polymérisation, UMR 140 CNRS/ESCPE, Bat 308 F, 43 Boulevard du 11 Novembre1918, BP 2077, 69616 Villeurbanne Cedex, France;2. Laboratoire de Chimie et Procédés de Polymérisation, UMR 140 CNRS/ESCPE, Bat 308 F, 43 Boulevard du 11 Novembre1918, BP 2077, 69616 Villeurbanne Cedex, FranceLaboratoire de Chimie et Procédés de Polymérisation, UMR 140 CNRS/ESCPE, Bat 308 F, 43 Boulevard du 11 Novembre1918, BP 2077, 69616 Villeurbanne Cedex, France;3. Service de RMN de la Fédération des Polyméristes Lyonnais, FR2151/CNRS, 69390 Vernaison, France;4. UMR 6517 (Chimie, Biologie et Radicaux Libres), Equipe Chimie Radicalaire, Organique et Polymères de Spécialité, CNRS/Universités d'Aix‐Marseille 1, 2 et 3, 13397 Marseille Cedex 20, France |
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Abstract: | A synthetic method for the production of polyethylene (PE) chains carrying alkoxyamine end‐group has been proposed first by successfully reacting the well‐known 2,2,6,6‐tetramethylpiperidine‐N‐oxyl (TEMPO) and N‐(2‐methyl‐2‐propyl)‐N‐(1‐diethylphosphono‐2,2‐dimethylpropyl)‐N‐oxyl (commonly called SG1) stable radicals with dipolyethylenylmagnesium compounds to give PE‐TEMPO and PE‐SG1. Since the homolytic cleavage of these two macroalkoxyamines for the production of block copolymers using controlled radical polymerization would require temperatures higher than 160 °C, two original new nitroxides (4‐(2,2‐dimethyl‐4‐(N‐tert‐Butyl‐N‐(1‐diethoxyphosphoryl‐2,2‐dimethylpropyl)aminoxy)‐4‐n‐butoxycarbonyl)butanoyloxyl]‐2,2,6,6‐tetramethylpiperidinyl‐1‐oxy, DD1) and 4‐(2,2‐dimethyl‐4‐(N‐tert‐Butyl‐N‐(1‐diethoxyphosphoryl‐2,2‐dimethylpropyl)aminoxy)‐4‐phenyl) butanoyloxyl]‐2,2,6,6‐tetramethylpiperidinyl‐1‐oxy, DD2) containing a TEMPO moiety and incorporating an SG1‐based alkoxyamine (cleavage temperature: 60 °C) were then synthesized. NMR analyses showed that the resulting PE‐DD1 and PE‐DD2 were obtained using this functionalization strategy though with low to moderate yields (from 17% to 40%). PE‐DD2 (40% functionalization) was used under controlled radical polymerization conditions of n‐butyl acrylate. SEC analyses together with 1H NMR analysis showed that a poly(ethylene‐b‐n‐butyl acrylate) block copolymer was produced and that the polymerization proceeded under control. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2705–2718, 2007 |
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Keywords: | block copolymers catalyzed chain growth controlled radical polymerization functionalization of polymers Nitroxide mediated polymerization polyethylene |
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