L. High, S. Holder, Hazel V. Penfold
Aug 30, 2007
Citations
0
Influential Citations
51
Citations
Journal
Macromolecules
Abstract
A free-base tetrabromoporphyrin, 15,20-tetrakis(4-(2-methyl-2-bromopropoxy)phenyl)-21H,23H-porphine (2), was synthesized in high yield (91%) by the esterification of 5,10,15,20-tetrakis(4-hydroxyphenyl)-21H, 23H-porphine (1) with 2-bromo-2-methylpropanoyl bromide. The free-base porphyrin (2) was demonstrated to be suitable as an initiator for atom transfer radical polymerization (ATRP) of methyl methacrylate giving porphyrin-core star-poly(methyl methacrylate) with conversions of up to 98% (CuIBr, N-(n-propyl)-2-pyridylmethanimine, toluene, 90 °C). UV−vis spectroscopic analysis demonstrated that a degree of complexation of Cu(II) by the porphyrin core occurred during the polymerization. To avoid Cu(II) complexation, zinc(II) 10,15,20-tetrakis(4-(2-methyl-2-bromopropoxy)phenyl)-21H,23H-porphine (4) was synthesized from the free-base porphyrin (2) and employed as an initiator in the ATRP of MMA, giving the corresponding Zn porphyrin-core star-PMMA. The free-base porphyrin (2) was also employed as an initiat...