「ネ ッ ト ワ ー ク ポ リ マ ー 」Vol.27 No.

4 (2006)
(218)

画団囮国
(Received June 15, 2006)

Synthesis of New Novolacs from Natural Phenolic Compounds

Chiho SAKAMOTO*,
Yoshiaki NAKAMOTO*,
Tadamasa NEMOTO**
and Gen-ichi KONISHI**

* Division of Material Engineering , Graduate School of

Natural Science & Technology, Kanazawa University
(Kakuma-machi, Kanazawa, Ishikawa 920-1192,Japan)
**Department of Organic & Polymeric Materials , Graduate School of
Engineering, Tokyo Institute of Technology
(Ookayama, Meguro-ku, Tokyo 152-8552,Japan)
Correspondence should be addressed to G. Konishi. Fax +81-3-5734-2888;Tel +81-3-5734-2321;
E-mail: gkonishi@polymer.titech.ac.jp

Synopsis

Thepreparationof new novolacsfrom naturalphenoliccompoundssuchas vinillylalcohol(2), o-vanillin(4),

eugenol(6), and 2-allylphenol(8) usingthe acid-catalyzed phenol-formaldehyde condensation
or self-condensation
is described.Theeugenolnovolac(7) waspreparedby thehydrochloric acid-catalyzed
polymerization
of eugenol(6)
withformaldehyde in goodyield.Thestructureof 7 wassupportedby its '1-1NMRand FT-IRspectra.Compound7,
whichhas a well-defined structurewassolublein THF,DMF,andacetone.Thepreparationof poly(vanillin) (3)by the
acid-catalyzedself-condensationof vanillylalcohol(2) is alsodiscussed.Thesepolymersarenewartificialpolyphenols
and expectedto be used as a medicine,antioxidant,etc. The functionalnovolacshavingthe ally!group(7,9)have
considerablematerialpotentialas a reactivepolymerandanadhesive.

1. Introduction
The novolacsderivedfrom natural phenoliccompoundshave been extensivelyinvestigated1-5). For example,Uyama
recentlyreportedthe preparationof polyphenolsfrom catechinand thier applicationas an anitioxidantwhichneutralizes
freeradicals(superoxide,nitricoxide and hydroxylradical) 2-4).
We alsoreportedthe poly(ferulicacid) 5).Thesepolymers
are a new class of artificialpolyphenols.It is importantto extend the scope of the phenolicpolymerstoward various
natural productsin materialviewpoints.
In this paper,we reportthe synthesisof solubleandwell-definednovolacderivativesfromnaturalphenoliccompounds,
suchas vinillylalcohol(2), o-vanillin(4), eugenol(6), and 2-ally1phenol(8).

2. Results and Discussion

2.1 Vanillin derivatives
The acid-catalyzedpolymerizationof vanillin (1) with formaldehydewas examined.Typicalprocedurewas as follows.

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The acetic acid solution containing 1 (1 equiv.) and formaldehyde (2 equiv.) was heated at 80 °C for 3 hours to give no
polymer. Although a prolonged reaction was carried out on the same condition, polymerization did not also proceed. This
is due to the steric hindrance and poor reactivity of 1.
The sulfuric acid-catalyzedself-condensationof 1 in bulk or in organicsolventssuch as acetic acid and 2-ethoxyethanoldid not
also occur.These resultsshowed a low reactivityof the formylgroup of 1 due to its electron-attractingproperty.(Scheme 1)

On the other hand, the poly(vanillin) (3)6)was successfully prepared from vanillyl alcohol (2) using the acid-catalyzed
self-condensation. The typical procedure (run 1) is as follows. An acetic acid solution (10 mL) of vanillyl alcohol (2)
(5 mmol), and conc. hydrochloric acid (37%) (1 mL) was stirred and heated at 60°C for 3 hours, then the reaction was
quenched by pouring it into a large amount of water. The resulting precipitate was then collected. The solid was dried
in vacuo to afford 3 in 74% yield. It is suggested that a
carbocation intermediate was efficiently generated from a
benzyl alcohol derivative. The obtained polymer (3) had
the same backbone (phenylenemethylene) of novolac.
The resulting polymer was quite-solublein tetrahydrofuran
(THF), dimethylformamide(DMF) and acetone. The structure
1
of the polymer was supported by its 1H NMR and FT-IR
Scheme 1 Polymerization of vanillin
spectra. The number average molecular weight (Me) was
found to be 900.(Scheme 2)

2 3
2.2 0-Vanillin
The polymerization of o-vanillin with formaldehyde
proceeded, but the obtained polymer (5) 7)had only a low
molecular weight. In the case of the hydrochloric acid
as a catalyst (run 1, 2), the yields of each polymer were
very small. It is noted that a strong acid (sulfuric acid) was
required for the successful polymerization. The remaining
formyl group on the polymer backbone was confirmed by

*The reaction time: 3h . its 11-1

NMR and FT-IR spectra. The formyl group of 4 is
less reactive than that of the formaldehyde due to electron-
Scheme 2 Self-condensation of vanillyl alcohol. donacity and steric hindrance. (Scheme 3)

2.3 Eugenol
The eugenol novolac was also obtained. The typical
procedure (run 1) is as follows. An acetic acid solution (10
4 5 mL) of eugenol (6) (5 mmol), paraformaldehyde (5 mmol
as formaldehyde), and conc. hydrochloric acid (37%) (1
mL, cat.) was stirred and heated at 60°C for 3 hours, then
the reaction was quenched by pouring it into a large amount
of water. The resulting precipitate was then collected. The
<m : f means <monomer : formaldehyde> molar ratio eugenol novolac (7) 8)was obtained in quantitative yield.
Scheme 3 Polymerization of o-vanillin. The resulting polymer was quite-soluble in

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tetrahydrofuran (THF), dimethylformamide (DMF) and acetone. The structure of the polymer was supported by its 'H
NMR and FT-IR spectra. The allyl group did not participate in the polymerization. From the GPC analysis, the Mn of 7
was found to be 1200. (Scheme 4)

2.4 2-Allylphenol
The polymerization of the 2-allylphenol (8) with formaldehyde efficiently proceeded on the same polymerization
condition of eugenol (6). The 2-allylphenol novolac (9) had a linear structure. (Scheme 5)
In the case of conc. sulfuric acid (98%) catalyst, the weight average molecular weight of 9 9)was found to be 20,000.
This high molecular weight novolac (9) has a significant potentials as precursors of cure and adhesive.

In conclusion,polyphenols from natural products were successivelyprepared using the acid-catalyzedphenol-formaldehyde

condensationor self-condensation.
In this study,acetic acid plays an importantrole in the successfulpolymerization.Acetic acid may
be used to advantagein generationand stabilizationof a carbocationintermediatefrom an aldehyde.These obtained polymersare
expectedto producenovelfunctions,such as medicines,antimicrobacterialmaterials,polymercomposite,etc.

Acknowledgement
This work was partially supported by the Industrial
Technology Research and Development Project (No.
04A23030) from NEDO of Japan.
6 7

References and Notes

1) P. L. Nayaka and S. Lenka, "Antibacterial Resins" in
PolymericMaterialEncyclopedia,CRCPress,p. 264 (1996).
2) J. E. Chung, M. Kurisawa, Y. J. Kim, H. Uyama, and S.
Kobayashi,Biomacromolecules, 5, 113(2004).
3) Y. J. Kim, J. E. Chung, M. Kurisawa, H. Uyama, and S.
Kobayashi,Biomacromolecules, 5, 474 (2004).
*reaction time: 3h . 4) Y. J. Kim, J. E. Chung, M. Kurisawa, H. Uyama, and S.
Kobayashi,Biomacromolecules, 5, 547(2004).
Scheme 4 Polymerization of eugenol. 5) C. Sakamoto, G. Konishi, Y. Nakamoto, K. Mizuno, ITE
Lett. Batt.NewTechMed.,6, 548 (2005).
6) Spectraldata of 3 (run 1): NMR (270MHz,CDC13, TMS)
6 6.2-6.8 (Ar), 3.4-4.0 (-0C143,Ar-C112-Ar);FT-IR (KBr)
3507(-OH),2937 (-OCH3,Ar-CH2-Ar)
7) Spectraldata of 5 (run 2): NMR(270MHz,CDC13, TMS)
6 9.8-10.0(-CHO),6.8-7.2(Ar), 5.0 (-OH),3.6-4.2 (-OCH3,
Ar-CH-Ar); FT-IR (KBr) 3420 (-OH), 2940 (-OCH3,Ar-
8
9 CH2-Ar),1654(C=0) cm-'.
8) Spectraldata of 7 (run 1): 'H NMR(270MHz,CDC13, TMS)
6 6.2-6.7 (Ar),4.8-5.2 (CH2-CH=CH2), 3.6-4.2 (-0013, Ar-
CH2-Ar),3.2 (Ar-C1-1_2-CH=CH2); FT-IR(KBr)3503 (-OH),
2939(-0CH3,Ar-CH2-Ar)cm'.
9) Spectraldata of 9 (run 1): 'H NMR(270MHz,CDC13,TMS)
6 6.6-7.1(Ar),4.9-5.2(CH2-CH=CH2), 3.7-3.9(Ar-CH-Ar),
3.2-3.4 (Ar-CH-CH=CH2);FT-IR(KBr) 3482 (-OH), 2922
(Ar-CH-Ar)
*reaction time: 3h .

Scheme 5 Polymerization of 2-allylphenol.

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