Ring‐opening polymerization of <i>rac</i>‐ and <i>meso</i>‐lactide initiated by indium bis(phenolate) isopropoxy complexes

Abstract

ABSTRACT Ring‐opening polymerization of rac ‐ and meso ‐lactide initiated by indium bis(phenolate) isopropoxides {1,4‐dithiabutanediylbis(4,6‐di‐ tert ‐butylphenolate)}(isopropoxy)indium ( 1 ) and {1,4‐dithiabutanediylbis(4,6‐di(2‐phenyl‐2‐propyl)phenolate)}(isopropoxy)indium ( 2 ) is found to follow first‐order kinetics for monomer conversion. Activation parameters Δ H ‡ and Δ S ‡ suggest an ordered transition state. Initiators 1 and 2 polymerize meso ‐lactide faster than rac ‐lactide. In general, compound 2 with the more bulky cumyl ortho ‐substituents in the phenolate moiety shows higher polymerization activity than 1 with tert ‐butyl substituents. meso ‐Lactide is polymerized to syndiotactic poly( meso ‐lactides) in THF, while polymerization of rac ‐lactide in THF gives atactic poly( rac ‐lactides) with solvent‐dependent preferences for heterotactic (THF) or isotactic (CH 2 Cl 2 ) sequences. Indium bis(phenolate) compound rac ‐(1,2‐cyclohexanedithio‐2,2′‐bis{4,6‐di(2‐phenyl‐2‐propyl)phenolato}(isopropoxy)indium ( 3 ) polymerizes meso ‐lactide to give syndiotactic poly( meso ‐lactide) with narrow molecular weight distributions and rac ‐lactide in THF to give heterotactically enriched poly( rac ‐lactides). © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51 , 4983–4991