An Improved Catalytic Method for Alkoxyamine Synthesis - Functionalized and Biradical Initiators for Nitroxide-Mediated Radical Polymerization

• Published in: Macromolecular rapid communications. Vol. 24; no. 10; pp. 609 - 613
• Main Authors: Bothe, Marc, Schmidt-Naake, Gudrun
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.07.2003; WILEY‐VCH Verlag; Wiley
• Subjects: alkoxyamine; Applied sciences; Exact sciences and technology; initiators; nitroxide; Organic polymers; Physical Sciences; Physicochemistry of polymers; Polymer Science; Polymerization; Preparation, kinetics, thermodynamics, mechanism and catalysts; radical polymerization; Science & Technology; synthesis; synthesis; EPOXIDATION CATALYSTS; alkoxyamine; STYRENE POLYMERIZATION; EFFICIENT SYNTHESIS; BLOCK; nitroxide; COPOLYMERS; initiators; radical polymerization; HIGH-YIELD SYNTHESIS; Radical catalyst; Free radical polymerization; Catalytic reaction; Nitroxyl; Bifunctional compound; Piperidine derivatives; Aryloxy complex; Chloro complex; Experimental study; Chemical synthesis; Manganese complex
• ISSN: 1022-1336; 1521-3927
• DOI: 10.1002/marc.200350002

Mn(salen)Cl was applied as a low‐cost catalyst for the formation of alkoxyamines from nitroxides and substituted styrenes. These “unimolecular initiators” for nitroxide‐mediated radical polymerization (NMRP) were synthesized using 2,2,6,6‐tetramethyl‐1‐piperidine‐1‐oxyl and 2,2,5‐trimethyl‐4‐phenyl‐3‐azahexane‐3‐oxyl. Functionalized alkoxyamines were obtained from 4‐vinylbenzyl chloride and 4‐vinylbenzyl alcohol. The divinyl compound 1,2‐bis(4‐vinylphenyl)ethane was converted to an alkoxyamine monomer and to bisaminooxy compounds, which can be used as “biradical initiators” for NMRP. Formation of alkoxyamines using Mn(salen)Cl as the catalyst.