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Living polymerization of methacrylic esters with aluminium porphyrin initiators. Axial ligand exchange activities of alkyl‐ and enolate‐aluminium porphyrins in relation to the polymerization Mechanism
Author(s) -
Aida Takuzo,
Sugimoto Hiroshi,
Kuroki Masakatsu,
Inoue Shohei
Publication year - 1995
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.610080408
Subject(s) - chemistry , polymerization , polymer chemistry , aluminium , porphyrin , alkyl , methyl methacrylate , copolymer , living polymerization , polymer , photochemistry , organic chemistry , radical polymerization
Polymerization of methacrylic esters such as benzyl methacrylate using as initiator an‐equimolar mixture of methylaluminium 5,10,15,20‐tetraphenylporphine [(TPP)AlMe] and 2,7,12,17‐tetramethyl‐3,8,13,18‐tetramethylporphine [(EtioP)AlMe] proceeded from both initiators, affording a unimodal polymer of narrow molecular weight distribution, although the reactivities of (TPP)AlMe and (EtioP)AlMe are very different from each other. 1 H NMR studies on a mixture of two different (porphinato)aluminium enolates, the growing species, and a mixture of a (porphinato)aluminium enolate and an alcoholate, in the absence and presence of methyl methacrylate (MMA or MMA‐ d 8 ), indicated an acyclic transition state polymerization mechanism by the participation of two aluminium porphyrin molecules, where the growing species always exchange their enolate ligands whenever it grows.