Photon Factory Activity Report 2005 #23 Part B (2006)
Applied Science

10C/2005G218

Synthesis and conformational properties of polymacromonomers consisting ofrod-like poly(n-hexyl isocyanate) macromonomers
Seigou KAWAGUCHI1*, Moriya KIKUCHI1, Yuji Jinbo2,2
1
Yoshinobu Izumi , and Katsutoshi Nagai
1
Department of Polymer Science and Engineering, Faculty of Engineering,
Yamagata University, Yonezawa 992-8510, Japan
2
Graduate Program of Human Sensing and Functional Sensor Engineering,
Graduate School of Science and Engineering, Yamagata University, Yonezawa 992-8510, Japan
Introduction
A macromonomer is any polymer or an oligomer
with a polymerizable functionality as an end group.
Formally, the macromonomer homopolymerizes to afford
a star- or comb-shaped polymer and copolymerizes withthe conventional monomer to give graft copolymer.
Recently, some interesting properties of poly(macromonomers) have been explored as a simple modelof brush polymers. However, most of macromonomer
used in these studies is limited to that consisting from theflexible chains.[1,2]scattered intensity was recorded by a position-sensitive
proportional counter (PSPC) with 512 channels over a-1
scattering vector range from 0.02 to 0.30 Å .
Thescattered vector was calibrated using a sixth peak of drycollagen.
Results and Discussion
Figure 1 shows double logarithmic plot of radius ofgyration, Rg of poly(VB-HIC-n) determined by SECMALS in THF with weight averaged degree ofpolymerization of the main-chain Nw. The Rg data forlinear polystyrene are plotted in the figure for comparison.
It can be seen clearly that Rg at fixed Nw increases withincreasing side chain length, most likely due to theincrease of chain stiffness.
The experimental data for poly(VB-HIC-n) could bequantitatively described in terms of the wormlike chain
model with the thickness and end effects. It is concluded
that the chain stiffness of the polymer is increased by thepresence of the rod-like side chains.

Scheme. Reaction schemes of rod-like macromonomers
and polymacromonomers.
In the present study, we report synthesis andconformational properties of the polymacromonomers,
consisting of a flexible polystyrene chain backbone androd-like PHIC side chains by SAXS, light scattering, [η]and AFM measurements in THF.
Experimental
Syntheses of polymacromonomers
The macromonomers (VB-HIC-n) were prepared byliving coordination polymerization of HIC in CH2Cl2 atroom temperature using titanium alkoxide complex as aninitiator, as shown in the scheme.[3] The homopolymer,
poly(VB-HIC-n)swerepreparedby
radicalhomopolymerization of VB-HIC-n using dimethyl 2, 2’azobis(2-methyl propionate) (V-601) as an initiator in nhexane at 60 °C and fractionated by repeating fractional
precipitation.
SAXS Measurements.
SAXS measurements ofpolymacromonomers were carried out in THF at 25 °C,
using BL-10C with a synchrotron orbital radiation as anX-ray source set up in the Photon Factory of the HighEnergy Accelerator Organization at Tsukuba, Ibaraki,
Japan. The wavelength of the X-ray was 1.488 Å. TheFigure 1. Dependence of the measured Rg on main-chain length(expressed in terms of the degree of polymerization) for poly(VBHIC-n) (n = 27, 46 and 75) in THF. The solid lines show thetheoretical values calculated from unperturbed cylinder worm-likechain model.

References[1] K. Ito et al. Adv. Polym. Sci. 142, 129(1999).
[2] S. Kawaguchi et al. Adv. Polym. Sci., 175, 317(2005).
[3] M. Kikuchi, et al. Des. Monom. Polym., 7, 603 (2004).
*skawagu@yz.yamagata-u.ac.jp

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