Synthesis and analysis of resorcinol-acetone copolymer

Article abstract of DOI:10.3390/molecules14010364

Synthesis and characterization of resorcinol-acetone copolymer is described. The polymer was prepared by trifluoroacetic acid-catalyzed polymerization of resorcinol with acetone. According to the ¹H-NMR, ¹³C-NMR, and MALDI-TOF Mass s

Full text of DOI:10.3390/molecules14010364

Molecules 2009, 14, 364-377; doi:10.3390/molecules14010364
OPEN ACCESS
molecules
ISSN 1420-3049
www.mdpi.com/journal/molecules
Article
Synthesis and Analysis of Resorcinol-Acetone Copolymer
Ataru Kobayashi and Gen-ichi Konishi *
Department of Organic & Polymeric Materials, Graduate School of Science & Engineering, Tokyo
Institute of Technology, SORST, Japan
* Author to whom correspondence should be addressed; E-mail: konishi.g.aa@m.titech.ac.jp.
Received: 27 November 2008; in revised form: 6 January 2009 / Accepted: 12 January 2009 /
Published: 13 January 2009
Abstract: Synthesis and characterization of resorcinol-acetone copolymer is described.
The polymer was prepared by trifluoroacetic acid-catalyzed polymerization of resorcinol
1
13
with acetone. According to the H-NMR, C-NMR, and MALDI-TOF Mass spectra data,
the obtained polymer had three types of repeating units: isopropylidene bridged-resorcinol,
chromane ring, and spiro-shaped double chromane ring, indicating that polymerization
proceeded via simultaneous addition-condensation and cyclization of resorcinol with
acetone. The obtained polymer can be useful not only for the development of plastic
materials such as thermosets, adhesives, and coatings but also for the synthesis of
biomaterials such as antimicrobial agents, pesticides, and medicines.
Keywords: Resorcinol; Acetone; Phenolic resin; Chromane ring; Addition-condensation;
Cyclization.
Introduction
Resorcinol is the 1,3-isomer of dihydroxyphenol and is used as a chemical intermediate for the
synthesis of pharmaceuticals, functional organic compounds, and polymer materials. In particular,
phenolic resins obtained from resorcinols have been extensively investigated. Resorcinol novolac
(RN) [1] and calixresorcinarenes (CRs) [2, 3] are the two well-known resins derived from resorcinol.
RN is a resorcinol-formaldehyde copolymer prepared using an acidic catalyst. It has many phenolic
hydroxy groups and an aromatic ring, both of which are highly reactive. Consequently, RN has been
extensively investigated for use in thermosets, adhesives, and as precursors for carbon materials [4].

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365
On the other hand, CRs are cyclic oligomers derived from the hydroalkylation product of resorcinol
and various alkyl or aryl aldehydes. CRs have hydrophobic cavities that can accommodate small
molecules or ions and therefore, CRs have been extensively investigated in host-guest chemistry and
analytical science [5, 6].
Figure 1. Resorcinol novolac and calix[4]resorcinarenes.
HO
OH
HO
HO
OH
OH
OH
HO
HO
R
R
HO
OH
OH
OH
OH
OH
R
R
HO
OH
HO
OH
OH
OH
HO
OH
OH
OH
OH
Resorcinol novolac (RN)
Calixresorcinarenes (CRs)
It would be useful to extend the applicability of RN in the field of material sciences by using other
carbonyl compounds such as acetone. However, to the best of our knowledge, a well-defined
resorcinol-acetone novolac has not yet been synthesized. While performing phenol-formaldehyde
condensation, it has been observed that the reactivity of acetone is lower than that of the aldehyde
because of steric hindrance. However, the use of phenol-acetone as a starting material, facilitates the
production of bisphenol A. The novolac obtained from acetone involves the isopropylidene bridge in
the polymer backbone, therefore, it should be more processable than a formaldehyde-based novolac [7-
9]. In this paper, we report the acid-catalyzed polymerization of resorcinol derivatives with acetone
and the characterization of the obtained polymers. These polymers are interesting from the viewpoint
of both polymer materials and bio-related materials.
Results and Discussion
Synthesis
To prepare resorcinol-acetone copolymer, we determined appropriate polymerization conditions
such as catalyst, solvent, and reaction temperature. The successful procedure for the preparation of
resorcinol-acetone copolymer is as follows (Scheme 1): trifluoroacetic acid was added dropwise to a
solution of resorcinol and excess acetone at 0˚C. After stirring the resulting solution for 12 h at room
temperature, it was poured into water and the precipitate was collected. Further purification was
carried out by reprecipitation in water. Polymer 1 was obtained as a colorless precipitate. The obtained
polymer was readily soluble in common organic solvents such as tetrahydrofuran (THF), chloroform,
and acetone. The result of the gel-permeation chromatography (GPC) analysis (eluent: THF;
polystyrene standards) showed that the weight-average molecular weight (Mw) of 1 was 3,700
(polydispersity index: Mw/Mn = 2.3). The molecular weight and yield of this polymer were not
dependent of the reaction temperature and polymerization time. For example, in the case of a higher
reaction temperature (60˚C) (Condition A) or a longer polymerization time (24 h) (Condition B),

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366
similar polymers (Condition A: Mw = 2,600, Mw/Mn = 1.8.; Condition B: Mw = 1,000, Mw/Mn = 1.3.)
were obtained.
Scheme 1. Synthesis of phenolic polymer 1.
HO
OH
HO
HO
O
HO
OH
O
O
TFA
rt, 12 h
O
+
n
l
m
A
B
C
The 1H-NMR, 13C-NMR, and FT-IR spectra of polymer 1 are shown in Figures 2-5, respectively. It
was very difficult to determine the structure of the polymer from these spectra as the polymerization of
resorciniol with acetone was complex. In a previous paper, it was reported that a chromane ring was
formed after the the reaction of resorcinol with acetone in dilute solution [10]. On the basis of a
previous study, we assumed that polymerization proceeded via simultaneous addition-condensation
and cyclization of resorcinol with acetone. Therefore, the obtained polymer 1 was composed of the
three types of repeating units (Unit A–C) as shown in Scheme 1.
MALDI-TOF mass study
In order to confirm the existence of the three types of repeating units, we measured the MALDI-
TOF mass spectrum (Figure 6). Fragmentation patterns of polymer 1 showed the presence of regular
peaks, which were formed according to the expression [m/z] = 150 Da (derived from A), 190 Da
(derived from B), and 230 Da (derived from C). Therefore, this result suggested that polymer 1 was
composed three different types repeating units (Units A–C).
Model compounds and assignments
In order to confirm the structure of the obtained polymer, we synthesized three model compounds,
namely, 2 (isopropylidene bridge), 3 (chromane ring), and 4 (spiro-shaped double chromane ring)
1
(Figure 7). Their structures were confirmed by the FT-IR, H-NMR, and 13C-NMR spectra. By
comparing the model compounds 2-4 with polymer 1, we confirmed the existence of the three
repeating units as follows.
Unit A: isopropylidene bridge
1
Because the H-NMR and 13C-NMR peaks of 1 were almost identical to those of 2, it was
confirmed that 1 contained an isopropylidene bridge structure. The observation of the upfield shift of
13
the C-NMR quaternary carbon (Ph-C(CH3)2-Ph) peak in 1 (30–31 ppm), as compared to that in 2
(40.5 ppm) showed that hydroxyl group were not attached to both the terminal benzene rings (Figures
3 and 4).

Molecules 2009, 14
Figure 2. 1H-NMR spectra of 1, 2, 3 (DMSO, 400 MHz), and 4 (MeOH, 400 MHz).
367
Ph-CH3
-CH2-
-CH3
4
3
2
1
Ph-H
-OH
Figure 3. 13C-NMR spectra of 1, 2, 3 (DMSO, 100 MHz), and 4 (MeOH, 100 MHz).
Ph-CH3
-CH2-
-CH3
4
O
C
O
O
Ph
3
2
1
C
Ph C Ph

Molecules 2009, 14
Figure 4. 13C-NMR spectra of 1, 2, 3 (DMSO, 100 MHz), and 4 (MeOH, 100 MHz).
368
2
4
3
1
1
Figure 5. FT-IR spectra of 1, 2, 3, and 4 (KBr).
4
3
2
1
4000
3500
3000
2500
2000
-1
1500
1000
500
wavenumer (cm )
Unit B: chromane ring; Unit C: spiro-shaped double chromane ring
From the NMR analysis, we also confirmed the existence of the chromane and spiro-shaped double
chromane rings in polymer 1. The 1H-NMR peaks of 1 were in good agreement with those of 3 and 4
13
(Figure 2). In particular, in the C-NMR spectra (Figures 3 and 4), three peaks at 44 (R-CH2-R), 77
(R-CH2-C(CH3)(OPh)-R), and 97 (R-CH2-C(OPh)2-CH2-R) ppm were found to be completely
consistent with those of 3 and 4, suggesting that 1 possessed chromane and spiro ring structures. It was
difficult to distinguish between Unit B and Unit C by analyzing the spectroscopic data.

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369
Figure 6. MALDI-TOF mass spectrum of polymer 1.
190 Da
230 Da
190 Da
150 Da
190 Da
230 Da
150 Da
150 Da
Figure 7. Model compounds 2, 3, and 4.
HO
OH
HO
OH
HO
O
HO
O
O
OH
4
2
3
Content of phenolic hydroxyl group
It was difficult to determine the ratio of each unit in the polymer by analyzing the spectroscopic
data. However, the phenolic hydroxyl group content of the polymer can be determined by
etherification. We therefore prepared the corresponding trimethylsilyl (TMS) derivatives of polymer 1
according to Scheme 2. From the FT-IR spectrum of the obtained polymer, it was observed that the
peak of the phenolic hydroxyl group completely disappeared; therefore, the polymer reaction had
1
proceeded quantitatively. From the H-NMR analysis, the integral ratio of the aromatic protons and
the trimethylsilyl group protons was found to be ca. 2:5. This result suggested that for every repeating
unit in polymer 1 there were 0.6 eq of hydroxyl groups. The numbers of hydroxyl groups contained in
Unit A, Unit B, and Unit C were 2, 1, and, 0, respectively, therefore, it can be assumed that a large
number of Unit Bs (chromane ring) and Unit Cs (double chromane ring) exist in the polymer. The
ratios of l, m, and, n of each repeating unit could not be determined in the present study.

Molecules 2009, 14
Scheme 2. Synthesis of TMS (trimethylsilyl group)-modified polymer.
370
TMSO
OTMS
TMSO
TMSO
O
O
Et3N
Polymer 1
TMS-Cl
+
O
CH2Cl2
rt, 45 h
n
l
m
High molecular weight polymer
In order to improve the processability of the obtained polymer, we tried to prepare a high molecular
weight polymer by acid-catalyzed addition-condensation of polymer 1 and formaldehyde. However,
the abovementioned reaction yielded a cross-linked insoluble gel. This is because the 2-position of the
resorcinol skeleton showed high reactivity for addition-condensation; therefore, a cross-linking
reaction efficiently proceeded under this reaction condition (see Experimental). Hence, to obtain a
high molecular weight polymer, we selected a 2-substituted resorcinol, i.e., 2-methylresorcinol as the
starting material. Polymer 5 (Mw = 2600, Mw/Mn = 1.7) was prepared by the same procedure as that
used to prepare polymer 1 using 2-methylresorcinol with acetone. Next, we successfully prepared an
organosoluble high molecular weight polymer by the reaction of polymer 5 with formaldehyde. The
obtained polymer was well soluble in THF and chloroform, and it exhibited a film-forming property.
The Mw of the polymer was found to be 94,000 (Mw/Mn = 4.3).
Scheme 3. Synthesis of high molecular weight polymer 6.
Figure 8. TG analysis of polymers 1, 5, and, 6.
100
80
60
40
20
1
5
6
0
100
200
300
400
500
Temperature (oC)

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Thermal properties
Differential scanning calorimetric (DSC) and thermogravimetric analyses (TGA) were carried out
to determine the thermal transition and degradation behavior of the obtained polymers. From the DSC
analysis, it was found that these polymers did not exhibit a glass transition temperature. From the TG
analyses of 1, 5, and, 6, the Td10 (10% loss in weight) was found to be 325, 281, and, 321˚C, and the
polymers exhibited high thermal stability under nitrogen atmosphere. The spiro-shaped structure of the
polymer backbone may be responsible for its thermal stability (Figure 8).
Conclusions
In conclusion, we have synthesized an organosoluble resorcinol-acetone copolymer in the presence
of acid catalyst. From the experimental results, especially the fragmentation patterns of the
corresponding MALDI-TOF mass spectrum, and a previous report [11], we concluded that the
obtained polymer consisted of the three types of repeating units, namely, isopropylidene-bridged
resorcinols, chromane rings, and spiro-shaped double chromane rings. Even though the structure of the
polymer was complex, it has a wide range of applications. The obtained polymer can be applicable not
only for the development of plastic materials [11-14] such as thermosets, adhesives, and coatings but
also for the synthesis of biomaterialss[15-25] such as antimicrobial agents, pesticides, and medicines.
Applications for the epoxy resin and the evaluation of the antimicrobial ability are now under study.
Experimental
General
Unless otherwise noted, all reagents and chemicals were used without further purification.
Paraformaldehyde (95%) and magnesium were obtained from Nacalai Tesque. 2-Methylresorcinol, 4-
tert-butylbenzoic acid methyl ester, and trimethylsilyl chloride were obtained from TCI. Resorcinol
1
and 4-methylresorcinol were obtained from Wako Pure Chem. and Aldrich, respectively. All the H-
13
NMR spectra (in DMSO-d6, CDCl3-d1, or CD3OD-d4) and the C-NMR spectra (in DMSO-d6 or
CD3OD-d4) were recorded on a 400 MHz JEOL LNM-EX400 instrument with tetramethylsilane
(TMS) as the internal standard. The FT-IR spectra were recorded using a JASCO FT-IR 460 plus
spectrometer. Gel permeation chromatography (GPC) was carried out by a JASCO UV-2070 detector
and a JASCO RI-2031 detector (TOSOH TSKgel G3000HXL or G4000HXL column) using
tetrahydrofuran (THF) as the eluent after calibration with polystyrene standards. Thermogravimetric
analysis (TGA) was performed using a SII TG/DTA 6200 machine (SEIKO Instrument Inc.) with a
heating rate of 10 °C/min under a nitrogen atmosphere. MALDI-TOFF mass was performed using
Shimadzu Biotech Axima ToG 2.7.2.
Preparation of resorcinol-acetone copolymer 1 and 2-methylresorcinol-acetone copolymer 5
Trifluoroacetic acid (98%, 10 mL) was added dropwise at 0˚C to a solution of resorcinol (5.5 g, 50
mmol) and an excess of acetone (15 mL). After stirring for 12 h at room temperature, the mixture was

Molecules 2009, 14
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poured into water (300 mL) and the precipitate formed was collected. The obtained polymer was
dissolved into minimum volume of acetone, and then the solution was reprecipitated in water (100
mL). The obtained polymer was dried in vacuo to give the polymer 1 (9.8 g). A similar polymerization
of 2-metylresorcinol afforded a corresponding polymer 5 (12.5 g). 1: Mn = 1,500, Mw = 3,700, Mw/Mn
1
= 2.3.; H-NMR (DMSO- d6, ppm): δ = 9.41-8.97 (-OH), 7.38-5.65 (Ph-H), 2.95-2.60, 2.12-0.31 (-
CH3, -CH2-); 13C-NMR (DMSO-d6, ppm): δ = 156.2-148.0, 127.1-120.3, 109.2, 105.0-96.3, 77.6-76.8,
47.6-44.9, 34.0-32.0, 30.8-27.9; IR (KBr, cm-1): ν = 3,420, 2,960, 2,870, 1,622, 1,490, 1,240, 1,140,
1,050.; 5: Mn = 1,500, Mw = 2,600, Mw/Mn = 1.7.; 1H-NMR (DMSO- d6, ppm): 9.13-8.76 (-OH), 8.62-
13
7.89, 7.25-5.89 (Ph-H), 3.01-2.63, 227-0.31 (-CH3, -CH2-); C-NMR (DMSO-d6, ppm): δ = 154.9-
149.4, 129.5-128.6, 124.2-119.5, 113.3-105.6, 78.4-77.5, 47.2-44.5, 33.9-27.5, 10.2-8.30.; IR (KBr,
cm-1): ν = 3,390, 2,960, 2,870, 1,610, 1,480, 1,430, 1,220, 1,080.
Syntheses of Model Compound 2 (Scheme 4)
Dry diethyl ether (100 mL) and iodomethane 5 mL (79 mmol) was added dropwise to magnesium
turnings (1.7 g, 70 mmol) in a flask at 0˚C. After stirring at room temperature for 0.5 h and then at
50˚C for 2 h, 4-tert-butylbenzoic acid methyl ester (3.8 mL, 20 mmol) was added at room temperature.
The resulting mixture was stirring at room temperature for 0.5 h and then at 50˚C for 1 h. After cooling
to room temperature, the resulting mixture was quenched with methanol (50 mL) and then 10%
aqueous HCl (50 mL). The mixture was extracted with diethyl ether (3×100 mL) and the combined
organic layer was dried over MgSO4. After removal of solvent, 2-(4-tert-butylphenyl)propan-2-ol was
1
obtained (3.85 g, >99% yield). H-NMR (CDCl3, ppm): δ = 7.43 (d, J = 8.8 Hz, 2H), 7.37 (d, J = 8.8
Hz, 2H), 1.56 (s, 6H), 1.32 (s, 9H); 13C-NMR (DMSO-d6, ppm): δ = 147.8, 147.4, 124.2, 124.1, 70.3,
33.8, 31.8, 31.1; IR (KBr, cm-1): ν = 3,340, 2,970, 2,860, 1,510, 1,460, 1,400, 1,360, 1,270, 1,170,
1,150, 1,130, 1,120, 960, 830.
Next, hydrochloric acid (12 N, 0.1 mL) was added dropwise at 0˚C to a solution of resorcinol (0.11
g, 1 mmol), 2-(4-tert-butylphenyl)propan-2-ol (0.36 g, 2 mmol) and acetic acid (3 mL). After stirring 9
h at room temperature, the mixture was extracted with 3×50 mL of diethylether. The solution was
concentrated under reduced pressure to afford the crude product. Futher purification was carried out by
1
recrystallization from hexane to give the model compound 2 (0.27 g, 60% yield). H-NMR (DMSO-
d6, ppm, Figure 9): δ = 8.44 (s, 2H), 7.21 (d, J = 8.4 Hz, 4H), 7.15 (s, 1H), 7.09 (d, J = 8.4 Hz, 4H),
13
6.09 (s, 1H), 1.60 (s, 12H), 1.25 (s, 18H); C-NMR (DMSO-d6, ppm, Figure 10): δ = 153.7, 148.4,
146.4, 125.2, 124.9, 124.3, 124.0, 104.5, 40.5, 33.7, 31.2, 29.5; IR (KBr, cm-1): ν = 3,500, 3,440,
3,380, 2,960, 2,870, 1,620, 1,510, 1,360, 1,270, 1,150, 1,120, 1,040, 830.
Scheme 4. Syntheses of Model Cmpound 2.

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Synthesis of model compound 3 (Scheme 5)
A mixture of resorcinol (6.6 g, 60 mmol), acetone (1.2 g, 20 mmol), hydrochloric acid (12 N, 2
mL), diethylether (100 mL), and CH2Cl2 (100 mL) was stirred and refluxed for 4 h. After removal of
solvents, the yellow oil was poured into water. This obtained precipitate was dried in vacuo for 24 h to
1
give the product 3 as colorless crystals (0.59 g, 20% yield). H-NMR (DMSO-d6, ppm, Figure 9): δ =
6.93 (d, J = 8.1 Hz, 1H), 6.83 (d, J = 8.5 Hz, 1H), 6.27-6.23 (m, 3H), 6.03 (d, J = 2.4 Hz, 1H), 6.01 (d,
J = 2.4 Hz, 1H), 2.90 (d, J = 13.9 Hz, 1H), 1.74 (d, J = 13.9 Hz, 1H), 1.56 (s, 3H), 1.14 (s, 3H), 0.65
13
(s, 3H); C-NMR (DMSO-d6, ppm, Figure 10): δ = 156.7, 156.1 , 154.5, 153.1, 127.0, 126.7, 121.9,
121.1, 108.2, 105.7, 103.2, 102.7, 77.1, 45.0, 32.7, 29.7, 29.5, 29.4; IR (KBr, cm-1): ν = 3,520, 3,340,
2,980, 2,960, 2,930, 1,620, 1,600, 1,510, 1,460, 1,310, 1,250, 1,160, 1,140, 1,000, 980, 840.
Scheme 5. Synthesis of Model Compound 3.
Synthesis of model compound 4 (Scheme 6)
Acetone (64 μL, 1.5 mmol), acetic acid (0.2 mL), and hydrochloric acid (12 N, 0.2 mL) were
added dropwise at 0˚C to a solution of 4-methylresorcinol (0.12 g, 1 mmol) and mercaptoacetic acid
(46 μL, 1 mmol). After stirring 13.5 h at 80˚C, the mixture was extracted with diethyl ether (3×50
mL). The organic layer was dried over Mg2SO4. The resulting solution was concentrated under
reduced pressure. The obtained residue was washed with an excess amount of acetone to afford the
1
model compound 4 (0.07 g, 19% yield). H-NMR (CD3OD, ppm, Figure 9): δ = 6.9 (s, 2H), 6.00 (s,
2H), 2.10 (s, 6H), 2.01 (d, J = 13.9 Hz, 2H), 1.89 (d, J = 13.9 Hz, 2H), 1.52 (s, 6H), 1.28 (s, 6H); 13C-
NMR (CD3OD, ppm, Figure 10): δ = 154.9, 150.4, 128.9, 123.6, 118.9, 104.3, 99.1, 48.1, 33.1, 32.8,
31.2, 15.7; IR (KBr, cm-1): ν = 3,530, 3,490, 3,430, 2,970, 2,930, 2,860, 1,620, 1,510, 1,410, 1,370,
1,280, 1,250, 1,180, 1,150, 1,060, 1,020, 1,000, 900.
Scheme 6. Synthesis of Model Compound 4.

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374
Figure 9. 1H-NMR spectra of 2, 3 (DMSO, 400 MHz), and 4 (MeOH, 400 MHz).
HO
OH
HO
OH
HO
O
HO
O
Hc
CH3
O
OH
Hb
CH3
Ha
CH3
Hb
H3C
Ha
H3C
Hc
Hb
H3C
Ha
3
2
4
Hb
Ha
Ha
Hc
Hc
Ha Ha
Ha
Hb
Hb
Hb
Figure 10. 13C-NMR spectra of 2, 3 (DMSO, 100 MHz), and 4 (MeOH, 100 MHz).
Cc
Cc
HO
OH
Cd
HO
OH
C
CH3
Ca
HO
O
HO
O
C
Cb
C
C
O
OH
CH3
C
CH3
Cb
bCd
C
Ce
Ca
Cd
C
Ce
Cc
H3C
H3C
Ca
2
3
4
Ce
Ca
4
Cb
Cb
Cd
Cc
Ce
3 Cc
Ce
Ca
Ca
Cd
Cb
Cb
2
Cc
Ca
Cd

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Preparation of high molecular weight polymer 6
2-Methylresorcinol-acetone copolymer 5 (0.98 g, 6.0 mmol) and paraformaldehyde (0.12 g, 3.0
mmol) were dissolved in acetic acid (8 mL) at room temperature. After stirring for a few minutes, the
mixture temperature drop to 0˚C and then hydrochloric acid (12 N, 1 mL) was added dropwise. After
stirring 12 h at 60˚C, the mixture was poured into water (100 mL) and the precipitate was collected.
Further purification was carried out by HPLC. The high molecular weight polymer 6 was obtained as a
colorless precipitate (0.97 g, 92% yield). Mn = 22,000, Mw = 94,000, Mw/Mn = 4.3.; 1H-NMR (DMSO-
d6, ppm): δ = 8.60-7.99, 7.17-6.26 (Ph-H), 3.88-3.53 (Ph-CH2-Ph), 2.96-2.60, 2.28-0.36 (-CH3, -CH2-);
IR (KBr, cm-1): ν = 3,400, 2,960, 2,930, 2,870, 1,610, 1,480, 1,440, 1,220, 1,080, 930.
TMS-modified polymer
To a solution of 1 (0.15 g) and Et3N (0.77 mL, 5.5 mmol) in CH2Cl2 (5 mL) was added TMSCl
(0.54 g, 5 mmol). After stirring at room temperature for 45 h, the mixture was extracted with
dichloromethane (3×50 mL). The solution was concentrated under reduced pressure to give the crude
product, which was dissolved in a minimum volume of acetone, and reprecipitated in methanol (50
mL). The obtained precipitate was dried in vacuo to give the TMS-modified polymer 1 (0.086 g). Mn =
1,300, Mw = 3,300, Mw/Mn = 2.5.; 1H-NMR (CDCl3, ppm): δ = 7.22-6.78, 6.62-5.81 (Ph-H), 2.82-2.62,
2.13-0.53 (-CH3, -CH2-), 0.40-0.095 (-SiCH3); IR (KBr, cm-1): ν = 3,390, 2,960, 2,870, 1,610, 1,480,
1,430, 1,220, 1,080.
Acknowledgements
This work was partially supported by SORST-JST and the Industrial Technology Research &
Development Grant (04A23030) from NEDO of Japan.
References and Notes
1. Konishi, G.; Precision polymerization of designed phenol: new aspects of phenolic resin
chemistry. J. Syn. Org. Chem. Jpn. 2008, 66, 705-713.
2. Timmerman, P.; Verboom, W.; Reinhoudt, D. N. Resorcinarenes. Tetrahedron 1996, 52, 2663-
2704.
3. V. Bohmer. Calixarenes, macrocycles with (almost) unlimited possibilities. Angew. Chem. Inr.
Ed. Engl 1995, 34, 713-745.
4. Al-Muhtaseb, S. A.; Ritter, J. A. Preparation and properties of resorcinol-formaldehyde organic
and carbon gels. Adv. Mater. 2003, 15, 101-114.
5. Aoyama, Y.; Tanaka, Y.; Toi, H.; Ogoshi, H. Polar host guest interaction – binding of nonionic
polar compounds with a resorcinol-aldehyde cyclooligomer as a lipophilic polar host. J. Am.
Chem. Soc. 1988, 110, 634-635.
6. Inouye, M.; Hashimoto, K.; Isagawa, K. Nondestructive Detection of Acetylcholine in Protic
Media: Artificial-Signaling Acetylcholine Receptors. J. Am. Chem. Soc. 1994, 116, 5517-5518.

Molecules 2009, 14
376
7. Wang, H. L.; Toppare, L.; Fernandes, J. E. Conducting polymer blends – polythiophene and
polypyrole blends with polystyrene and poly(bisphenol-A carbonate). Macromolecules 1990, 23,
1053-1059.
8. Varnell, D. F.; Runt, J. P.; Coleman, M. M. Fourier-transform infrared studies of polymer blends
6. further observations on the poly(bisphenol-A carbonate)-poly(epsilon-caprolactone) system.
Macromolecules 1981, 14, 1350-1356.
9. Nemoto, T.; Konishi, G.; Arai, T.; Takata, T. Synthesis and Properties of Fluorine-Containing
Poly(arylenemethylene) as a New Heat-Resistant Denatured Phenolic Resin. Polym. J. 2008, 40,
622-628.
10. Livant, P.; Webb, T. R.; Weizheng Xu. Reaction of resorcinol with acetone. J. Org. Chem. 1997,
62, 737-742.
11. Kadota, J.; Fukuoka, T.; Uyama, H.; Hasegawa, K.; Kobayashi, S. New positive-type photoresists
based on enzymatically synthesized polyphenols. Macromol. Rapid Commun. 2004, 25, 441-444.
12. Jeerupan, J.; Konishi, G.; Nemoto, T.; Shin, D.-M.; Nakamoto, Y. Synthesis of Multifunctional
Poly(calix[4]resorcinarene). Polym. J. 2007, 39, 762-763.
13. Nemoto, T.; Ueno, T.; Nishi, M.; Shin, D.-M.; Nakamoto, Y.; Konishi, G. Synthesis and
Properties of Organosoluble Poly(phenylenemethylene)s from Substituted Benzenes or
Naphthalenes. Polym. J. 2006, 38, 1278-1282.
14. Kimura, T.; Nakamoto, Y.; Konishi, G. Preparation of Organic/Inorganic Polymer Hybrid from a
New Class of Novolac. Polym. J. 2006, 38, 606-609.
15. Chung, J. E.; Kurisawa, M.; Kim, Y. J.; Uyama, H.; Kobayashi, S. Amplification of antioxidant
activity of aatechin by polycondensation with acetaldehyde. Biomacromolecules 2004, 5, 113-
118.
16. Tsujimoto, T.; Uyama, H.; Kobayashi, S. Curing Behaviors of Crosslinkable Polynaphthols from
Renewable Resources: Preparation of Artificial Urushi. Macromolecules 2004, 37, 1777-1782.
17. Turkmen, N.; Velioglu, Y. S.; Sari, F.; Polat, G. Effect of extraction conditions on measured total
polyphenol contents and antioxidant and antibacterial activity of black tea. Molecules 2007, 12,
484-496.
18. Kubo, I.; Nitoda, T.; Nihei, K. Effects of Quercetin on Mushroom Tyrosinase and B16-F10
Melanoma Cells. Molecules 2007, 12, 1045-1056. 11.
19. Kadoma, Y.; Fujisawa, S. A Comparative Study of the Radical-scavenging Activity of the
Phenolcarboxylic Acids Caffeic Acid, p-Coumaric Acid, Chlorogenic Acid and Ferulic Acid,
With or Without 2-Mercaptoethanol, a Thiol, Using the Induction Period Method. Molecules
2008, 13, 2488-2499.
20. Mao, Z.; Zheng, Y. L.; Zhang, Y. Q.; Han, B. P.; Zhu, X. W.; Chang, Q.; Hu, X. B. The Anti-
apoptosis Effects of Daidzein in the Brain of D-Galactose Treated Mice. Molecules 2007, 12,
1455-1470.
21. Yang, D. P.; Ji, H. F.; Tang, G. Y.; Ren, W.; Zhang, H. Y. How Many Drugs Are Catecholics.
Molecules 2007, 12, 878-884.
22. Li, J.; Jiang, Y. Litchi Flavonoids: Isolation, Identification and Biological Activity. Molecules
2007, 12, 745-758.

Molecules 2009, 14
377
23. Mikame, K.; Funaoka, M. Polymer Structure of Lignophenol I —Structure and Function of
Fractionated Lignophenol—. Polym. J. 2006, 38, 585-591.
24. Mikame, K.; Funaoka, M. Polymer Structure of Lignophenol II —Comparison of Molecular
Morphology of Lignophenol and Conventional Lignins—. Polym. J. 2006, 38, 592-596.
25. Mikame, K.; Funaoka, M. Conversion and Separation Pattern of Lignocellulosic Carbohydrates
through the Phase-separation System. Polym. J. 2006, 38, 694-702.
Sample Availability: Available from GK.
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