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Polymerization of Bulky of Oxirane Monomers Leading to Polyethers Exhibiting Intramolecular Charge Transfer Interactions
Author(s) -
Merlani Maia,
Song Zhiyi,
Wang Yuting,
Yuan Yuehui,
Luo Jiyue,
Barbakadze Vakhtang,
Chankvetadze Bezhan,
Nakano Tamaki
Publication year - 2019
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.201900331
Subject(s) - monomer , cationic polymerization , chemistry , polymer chemistry , intramolecular force , polymer , side chain , polymerization , chain transfer , kinetic chain length , pendant group , photochemistry , radical polymerization , stereochemistry , organic chemistry
Three novel oxirane monomers, 2‐methoxycarbonyl‐3‐(3,4‐dibenzyloxyphenyl)oxirane (MDBPO), 2‐benzyloxycarbonyl‐3‐(3,4‐dibenzyloxyphenyl)oxirane (BDBPO), and 2‐ t ‐butyloxycarbonyl‐3‐(3,4‐dibenzyloxyphenyl)oxirane (TBDBPO) are prepared and polymerized using BF 3 ‐OEt 2 in CH 2 Cl 2 to yield polyethers. The monomers smoothly lead to polymers under the cationic conditions in spite of the monomers' rather bulky structures. The obtained polymers exhibit characteristic UV spectra with intramolecular charge transfer (ICT) bands through hetero π‐stacked structure formed between the side‐chain carbonyl group and the phenyl group directly connects to the main chain. The relative intensity of the ICT bands is the strongest for poly(TBDBPO) having bulky t ‐butyl ester group. This spectral feature is considered to have connection with rigidity of polymer chain. Poly(TBDBPO) having the bulkiest side‐chain group is considered to possess the most rigid chain conformation that can account for its strongest ICT interactions that may occur between the carbonyl group and the phenyl group directly attached to the main chain. The proposed rigid chain conformation of poly(TBDBPO) is supported by the fact that the polymer does not show clear T g while the other two polymers do.