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Stereospecific anionic polymerization of chiral benzyl α‐[(1‐phenylethoxy)methyl]acrylate
Author(s) -
Uno Takahiro,
Habaue Shigeki,
Okamoto Yoshio
Publication year - 1998
Publication title -
chirality
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.43
H-Index - 77
eISSN - 1520-636X
pISSN - 0899-0042
DOI - 10.1002/(sici)1520-636x(1998)10:7<711::aid-chir18>3.0.co;2-2
Subject(s) - chemistry , tacticity , monomer , polymerization , polymer chemistry , anionic addition polymerization , radical polymerization , polymer , methyl acrylate , stereospecificity , chirality (physics) , copolymer , acrylate , kinetic chain length , solution polymerization , specific rotation , photochemistry , organic chemistry , catalysis , chiral symmetry breaking , physics , quantum mechanics , nambu–jona lasinio model , quark
A novel chiral monomer, benzyl α‐[(1‐phenylethoxy)methyl]acrylate was synthesized, and the stereoregularity and chiroptical property of the polymers obtained by radical and anionic polymerizations were investigated. Anionic polymerization in toluene provided a polymer with high isotacticity regardless of optical purity of the monomer and difference of counter cations, Li + and Mg 2+ , while radical polymerization appears to yield an atactic polymer. The isotactic copolymers anionically obtained from a mixture of ( R )‐ and ( S )‐monomers showed peak splitting probably due to the triad arrangement of ( R ) and ( S ) groups of side chains in the resonance of 13 C‐NMR spectra. The isotactic polymer prepared from enantiomerically pure ( R )‐monomer ([α] 25 365 = +157°) with n ‐BuLi in toluene exhibited higher specific rotation ([α] 25 365 = +262°) than that of the radical polymer ([α] 25 365 = +162°). This may be explained by regular arrangement of optically active groups along the polymer chain of the isotactic polymer. Chirality 10:711–716, 1998. © 1998 Wiley‐Liss, Inc.