142 Advances in Polymer Science Editorial Board: A. Abe. A.-C ...

152 K. Ito, S. Kawaguchi
Fig. 4. Double logarithmic plots of z 1/2 vs Mw of poly(macromonomer) of 26 (m=4, n=
50) in 0.05 N NaCl H 2O at 25 ˚C. Open symbols (o) are experimental results. The closed symbols
(l) are calculated values by Eqs. (5) and (6). The thick solid line is theoretical, calculated
from Eqs. (11) and (14–17) for the perturbed KP chain with q=17 nm, M L =1.03´10 4 nm –1 ,
and B=5.78 nm; the dashed line is theoretical, calculated for the unperturbed KP chain (B=0)
verse S-shaped curve. That is, in the M w lower than ca. 1´10 5 , the polymacromonomer
assumes a star-shaped conformation and above it the characteristic bottlebrush
conformation of the polymacromonomer appears.
With M w higher than 3´10 5 , the experimental points could be fitted by a
smooth convex curve. The slope of the convex curve was about 1.54 for M w between
5´10 5 and 1´10 6 and about 1.15 for M w between 3´10 6 and 3´10 7 . This
change in slope implies that the molecule is rodlike at lower MW and approaches
a spherical coil as M w increases, which is the characteristic behavior of semiflexible
polymers.