Macromolecules, Vol. 37, No. 5, 2004
Cross-Linkable Polynaphthols 1781
mers having an unsaturated group derived from natural
oils. During the polymerization using Fe-salen catalyst,
only the naphthol moiety was exclusively reacted to give
soluble polynaphthols in high yields. The resulting
polymers were cured by thermal treatment or cobalt
naphthenate catalyst to give the brilliant film (“artificial
urushi”) with high hardness and gloss surface.
Recently, polymeric materials from renewable natural-
based substrates have worldwide received much atten-
tion in social and environmental viewpoints, since their
use contributes to global sustainability without deple-
2
1
tion of scare resources. The present study provides a
new route of high-performance coatings from renewable
abundant triglycerides. Further studies on synthesis of
useful polymeric materials from natural oils are under
way in our laboratory.
Ack n ow led gm en t. This work was partly supported
by Program for Promotion of Basic Research Activities
for Innovative Bioscience and by the 21st century COE
program, COE for a United Approach to New Materials
Science. We thank Dr. H. Oyabu and Mr. N. Ando
F igu r e 3. Dynamic viscoelasticity of the cross-linked film
from poly(1a ) with thermal treatment.
(
Kyoto Municipal Institute of Industrial Research) for
the dynamic mechanical analysis.
Refer en ces a n d Notes
(
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F igu r e 4. FT-IR spectra of (A) poly(1a ) and (B) the cured film
from poly(1a ) by cobalt naphthenate catalyst.
1
996; p 225.
(
3) (a) Majima, R. Ber. Dtsch. Chem. Ges. 1909, 42B, 1418. (b)
Majima, R. Ber. Dtsch. Chem. Ges. 1922, 55B, 172. (c)
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of dissipation factor (tan δ) clearly suggests the homo-
geneous structure of the film. In high-temperature
region, E′ was constant, suggesting that almost all of
unsaturated groups in the side chain were reacted and
the film possessed a high thermal stability.
(
4) (a) Ikeda, R.; Tsujimoto, T.; Tanaka, H.; Oyabu, H.; Uyama,
H.; Kobayashi, S. Proc. J pn. Acad. 2000, 76B, 155. (b)
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Figure 4 shows FT-IR spectra before and after the
curing of the film from poly(1a ). The prepolymer had a
7
4, 1067. (d) Kobayashi, S.; Uyama, H.; Ikeda, R. Chem.s
Eur. J . 2001, 7, 4754.
-
1
characteristic peak at 3010 cm
ascribed to C-H
(
(
(
5) (a) Tsujimoto, T.; Ikeda, R.; Uyama, H.; Kobayashi, S. Chem.
Lett. 2000, 1122. (b) Tsujimoto, T.; Ikeda, R.; Uyama, H.;
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stretching of the inner olefin moiety. After the curing,
this peak completely disappeared. The cross-linking
4
reaction of the unsaturated moiety in the side chain was
also observed by change of characteristic C-H bending
-
1
peaks at 994, 976, and 730 cm , which are ascribed to
the conjugated cis-trans double bond, nonconjugated
trans double bond, and nonconjugated cis double bond,
4
respectively. The gradual decrease of the peak at 730
2
11.
8) (a) Hovorka, M.; Zavad, A. J . Tetrahedron 1992, 48, 9517.
b) Noji, M.; Nakajima, M.; Koga, K. Tetrahedron Lett. 1994,
-
1
cm was observed, whereas the peak intensity at 976
(
cm gradually increased. The peak at 994 cm-1 became
-1
(
larger at the early stage of the curing and afterward
35, 7983. (c) Amou, S.; Takeuchi, K.; Asai, M.; Niizeki, K.;
Okada, T.; Seino, M.; Haba, O.; Ueda, M. J . Polym. Sci., Part
A: Polym. Chem. 1999, 37, 3709.
smaller. Furthermore, a peak at 1075 cm-1 newly
appeared, which is due to C-O-C stretching of the
resulting cross-linked moiety. A broad peak ascribed to
O-H stretching became larger, which is due to the
formation of the hydroxy-terminated polymer. Similar
spectral changes were observed in the curing of other
prepolymers. These suggest that the cross-linking mech-
anism is similar to that of oil autoxidation.20
(
9) (a) Dordick, J . S.; Marletta, M. A.; Kilibanov, A. M. Biotech-
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Con clu sion
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1
Novel cross-linkable polynaphthols were synthesized
by the oxidative polymerization of the naphthol mono-
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