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Synthetic and mechanistic aspects of anionic polymerization of (METH)acrylates initiated by metal‐free salts of CH‐acidic compounds
Author(s) -
Reetz Manfred T.,
Hütte Stephan,
Goddard Richard
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.610080406
Subject(s) - chemistry , polymerization , phenylacetic acid , polymer chemistry , anionic addition polymerization , living anionic polymerization , malonic acid , ionic polymerization , methacrylate , polymer , organic chemistry , radical polymerization
The tetrabutylammonium salts of CH‐acidic compounds (malonic acid diesters and diamides, nitropropane, phenylacetic and phenylpropionic acid esters and 9‐ethyltfuorene) serve as inexpensive initiators for the anionic polymerization of acrylates and methacrylates at room temperature. Molecular weights of 1500–25,000 can be reached, the molecular weight distributions being fairly narrow ( D = 1·1–1·4 in optimized cases). Side‐reactions as monitored by GC analyses include backbiting and Hofmann elimination, which means that the process is not a true living polymerization. The x‐ray structural analyses of the tetrabutylammonium salts of phenylacetic and 2‐phenylpropionic and 2‐phenylbutyric acid esters show that anions and cations interact with one another via hydrogen bonding. Therefore, the initiators cannot be considered to be naked anions, a conclusin which very likely also applies to the growing polymer chain end during polymerization.