Synthesis of meth(acrylate) diblock copolymers bearing a fluorescent dye at the junction using a hydroxyl-protected initiator and the combination of anionic polymerization and controlled radical polymerization
Jd. Tong et al., Synthesis of meth(acrylate) diblock copolymers bearing a fluorescent dye at the junction using a hydroxyl-protected initiator and the combination of anionic polymerization and controlled radical polymerization, MACROMOLEC, 34(4), 2001, pp. 696-705
The synthesis of well-defined poly(methyl methacrylate)-b-poly(alkyl acryla
te) diblock copolymers with a single fluorescent dye molecule (phenanthrene
or anthracene) at the junction was investigated. The first block was prepa
red by the anionic polymerization (AP) of(meth)acrylate in THF at -78 degre
esC, using the 3-(tert-butyldimethylsilyloxy)-1-propryl (aryl = 2-phenanthr
yl or 2-anthryl) monoadduct as the initiator. After the end group of the fi
rst block was transformed into alpha -bromoester, the diblock copolymer was
formed by the atom transfer radical polymerization (ATRP) of the second me
thacrylate monomer using the first block as the initiator. The block copoly
mers were characterized by GPC, UV, and NMR. We found that the synthesis of
anthracene-labeled diblock copolymer was perturbed by the reaction of the
propagating poly(alkyl acrylate) radical with anthracene. Consequently, thi
s synthesis has to start from the anionic polymerization of tert-butyl acry
late, followed by chain extension to poly(methyl methacrylate) by ATRP.