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A novel observation in anionic ring‐opening polymerization behavior of cyclic carbonates having aromatic substituents
Author(s) -
Matsuo Jyuhou,
Sanda Fumio,
Endo Takeshi
Publication year - 1998
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/(sici)1521-3935(19981101)199:11<2489::aid-macp2489>3.0.co;2-v
Subject(s) - alkoxide , polymerization , polymer chemistry , chemistry , monomer , anionic addition polymerization , ring opening polymerization , copolymer , ring (chemistry) , depolymerization , polymer , organic chemistry , catalysis
The anionic ring‐opening polymerization of six‐membered cyclic carbonates having aromatic substituents, 5‐methyl‐5‐phenyl‐1,3‐dioxan‐2‐one ( 1 ) and 5,5‐diphenyl‐1,3‐dioxan‐2‐one ( 2 ), was carried out. The anionic homopolymerization of 1 readily proceeds to afford the corresponding polycarbonate, while 2 showed only a slight homopolymerizability. This is due to a rapid back biting reaction of the propagating polymer end to form 2 . The conformational restriction of the adduct of 2 with an alkoxide, originating from the electrostatic repulsion between the alkoxide anion and the π electrons of the aromatic rings, might cause the rapid back biting reaction. The anionic copolymerization of 2 with 5,5‐dimethyl‐1,3‐dioxan‐2‐one ( 3 ) proceeds to afford the copolymer. The anionic ring‐opening polymerization of 1 was confirmed to be an equilibrium polymerization. Monomer 1 was regenerated up to the equilibrium monomer concentration by depolymerization of poly( 1 ). A volume expansion (10.8%) was observed during the polymerization of 1 .