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Relative importance of side reactions in the RLi‐acrylonitrile — dimethylformamide system
Author(s) -
Denisov Viktor M.,
Yakimansky Alexander V.,
Novoselova Anna V.,
Erussalimsky Boris L.
Publication year - 1995
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.1995.021960404
Subject(s) - acrylonitrile , chemistry , polymer chemistry , exothermic reaction , dimethylformamide , butyllithium , anionic addition polymerization , formamide , polymerization , organic chemistry , solvent , polymer , copolymer
The probability of interaction of anionically growing poly(acrylonitrile) chains with dimethyl‐formamide (DMF) in the acrylonitrile (AN)‐RLi‐DMF system was investigated by means of NMR data, poly(acrylonitrile) synthetized with various ROLi initiators does not contain traces of DMF fragments. Quantum chemical calculations were carried out taking CH 3 CH 2 CH(CN)Li as a model compound and simulating the anionic active site of AN. The results obtained show that the interaction of this compound with AN is highly preferred (by 100 kJ/mol) to that with DMF. Qualitatively similar results are related to the butyllithium(BuLi)‐AN and BuLi‐DMF systems. However, the reaction between BuLi and DMF is exothermic (in contrast to that between the active site of the model compound with DMF). This fact is in agreement with the effective addition of BuLi to DMF in the absence of any competing compound.