Surface modification of poly(GMA-co-EDMA-co-MMA) with resorcarenes

Article abstract of DOI:10.21577/0103-5053.20180074

Surface modification of poly(GMA-co-EDMA-co-MMA), whose synthesis was performed by copolymerization of 2,3-epoxypropyl methacrylate (GMA), methyl methacrylate (MMA), and ethylene glycol dimethacrylate (EDMA), was compared between aliphatic and aromatic su

Full text of DOI:10.21577/0103-5053.20180074

http://dx.doi.org/10.21577/0103-5053.20180074
J. Braz. Chem. Soc., Vol. 29, No. 9, 1965-1972, 2018
Printed in Brazil - ©2018 Sociedade Brasileira de Química
Article
Surface Modification of Poly(GMA-co-EDMA-co-MMA) with Resorcarenes
Alver A. Castillo-Aguirre,a Betty A. Velásquez-Silva,a Cindy Palacio,a Frank Baez,a
Zuly J. Rivera-Monroya and Mauricio Maldonado*,a
aDepartamento de Química, Facultad de Ciencias, Universidad Nacional de Colombia,
Sede Bogotá, Carrera 30 No. 45-03, 11001 Bogotá, Colombia
Surface modification of poly(GMA-co-EDMA-co-MMA), whose synthesis was performed
by copolymerization of 2,3-epoxypropyl methacrylate (GMA), methyl methacrylate (MMA),
and ethylene glycol dimethacrylate (EDMA), was compared between aliphatic and aromatic
substituted resorcarenes. The copolymer surface was modified by reacting with resorcarenes,
and the vibrational properties of the modified copolymers were investigated via attenuated total
reflectance Fourier transform infrared (ATR-FTIR) and Raman spectroscopies in dry state at room
temperature. Those analysis showed that only tetra(p-hydroxyphenyl)resorcarene was linked to the
copolymer, the reaction was regioselective with the crown conformer. Additionally, quantification
of incorporated macrocyclic was performed, specifically, the maximum fixation of resorcarene in
the copolymer was 95% when employing two molar resorcarene excesses per glycidyl residue.
The modification was carried out in both acidic and basic medium and it was established that the
polymer is modified with the aromatic resorcarene only in basic medium, while the reaction in
basic medium with aliphatic resorcarenes produces their corresponding tetrasodium salt.
Keywords: resorcarene, surface modification, copolymerization, open chain reaction
Introduction
bound to multiple surface types. Thus resorcarenes are
used in high performance liquid chromatography (HPLC)
for modification of the stationary phase, and the process
involves the lower rim of the resorcarene derivate with polar
carbonate groups covalently bonded to a silica substrate.16
Resorcarenes covalently linked by their upper rim to silica
particles, which have been used as new stationary phases
((3-(C-methylcalix[4]resorcinarene)-2-hydroxypropoxy)-
propylsilyl-appended silica particles (MCR-HPS) and
bromoacetate-substituted MCR-HPS particles (BAMCR-
HPS)), have been also reported.17
For surface modification, the use of 2,3-epoxypropyl
methacrylate (GMA) copolymers has been continuously
growing, due to their successful applications in various
process.18-21 Copolymers of GMA are commercially
available, bearing reactive oxirane groups. These oxirane
groups present in the polymer chain can easily undergo an
opening reaction with nucleophilic reagents that contain
hydroxyl, carboxyl or amine groups.22-24
Interest in polymer surface modifications using
macrocyclic systems has increased in recent years. As an
example, the use of macrocyclic ligands such as crown ethers1
or calixarenes2 in the surface modification of stationary
phases for analytical separations can be mentioned. In this
field, the use of resorcarenes as a macrocyclic molecules for
surface modification has made a significant contribution to
the development of new applications, including separation
techniques and heterogeneous catalysts, among others.
Resorcarenes represent a class of macrocyclic phenolic
compounds obtained from the condensation reaction of
resorcinol with several aldehydes in acidic solutions,3
and they can be modified with various substituents on the
upper and lower rim to provide specific functionality and
selectivity. The many possible structural variations lead to
potential applications as voltammetric sensors,4 dendrimer
synthesis,5,6 dyeing of fibers,7,8 nuclear magnetic resonance
(NMR) solvating agents,9,10 chemical receptors for molecules
and ions11-13 and absorption of heavy metal ions,14,15 besides,
resorcarene derivatives can be absorbed or covalently
To continue with our studies related to the
chemical reactivity of resorcarenes, in the present
investigation the reaction efficiency of the glycidyl
residue, in poly(2,3-epoxypropyl methacrylate-co-
ethylene glycol dimethacrylate-co-methyl methacrylate)
*e-mail: mmaldonadov@unal.edu.co

1966
Surface Modification of Poly(GMA-co-EDMA-co-MMA) with Resorcarenes
J. Braz. Chem. Soc.
(poly(GMA-co-EDMA-co-MMA)), is evaluated using
some resorcarenes, specifically, tetrapropylresorcarene (1),
tetrabutylresorcarene (2), tetrapentylresorcarene (3)
and tetra(p-hydroxyphenyl)resorcarene (4). Modified
copolymers were analyzed via attenuated total reflectance
Fourier transform infrared spectroscopy (ATR-FTIR) and
Raman spectroscopy in the dry state at room temperature.
This showed that only tetra(p-hydroxyphenyl)resorcarene
was linked to the copolymer. It was found that the
glycidylmethacrylate oxirane opening reaction by using
tetra(p-hydroxyphenyl)resorcarene proceeds selectively
at the lower rim hydroxyl group without a reaction of the
upper rim hydroxyl groups, observing that this trend in solid
phase is similar to that observed in solution.25
solid material formed was filtered and washed with water to
remove traces of acid. The filtrate was dried under vacuum
and was characterized by IR and 1H NMR.
Tetrapropylresorcarene (1)
It was obtained as yellow solid in yield 82%;
mp > 250 °C decomposition; FTIR (KBr) n / cm-1 3318
(O–H), 1202 (C–O); 1H NMR (400 MHz, DMSO-d6) d 0.90
(t, 12H, CH3), 1.20 (m, 8H, CH2), 2.08 (q, 8H, CH2), 4.23
(t, 4H, CH), 6.15 (s, 4H, ortho to OH), 7.24 (s, 4H, meta
to OH), 8.94 (s, 8H, OH).
Tetrabutylresorcarene (2)
It was obtained as pale yellow powder in yield of 87%;
mp > 250 °C decomposition; FTIR (KBr) n / cm-1 3314
(O–H), 1194 (C–O); 1H NMR (400 MHz, DMSO-d6) d 0.90
(t, 12H, CH3), 1.23 (m, 16H, (CH2)2), 2.11 (q, 8H, CH2),
4.23 (t, 4H, CH), 6.15 (s, 4H, ArH, ortho to OH), 7.26 (s,
4H, ArH, meta to OH), 8.94 (s, 8H, OH).
Experimental
General information
All chemical reagents were acquired from commercial
suppliers and used without further purification. The
structures of resorcarenes were confirmed by NMR
spectroscopy. Raman spectra were recorded on a Thermo
Scientific DXR Raman microscope with the Raman shift
in cm-1. A Thermo Fisher Scientific Nicolet iS10 FT-IR
spectrometer was used for collecting ATR-FTIR spectra
Tetrapentylresorcarene (3)
It was obtained as yellow solid in yield 98%;
mp > 250 °C decomposition; FTIR (KBr) n / cm-1 3415
(O–H), 1292 (C–O); 1H NMR (400 MHz, DMSO-d6) d 0.69
(t, 12H, CH3), 1.19 (br s, 24H, (CH2)3), 1.93 (m, 8H, CH2),
4.19 (br s, 4H, CH), 6.22 (s, 4H, ArH, ortho to OH), 7.22
(s, 4H, ArH, meta to OH), 9.02 (s, 8H, OH).
1
in the region of 600-4000 cm-1. H NMR spectra were
recorded in DMSO-d6 at 400 MHz on a BrukerAvance 400
instrument. Chemical shifts are reported in ppm, using the
residual solvent signal as reference. Thermogravimetric
analysis coupled with differential scanning calorimetry
(TGA/DSC) was carried out on a Mettler Toledo
(TGA/DSC 3+) simultaneous thermal analyzer. 10 mg of
each compound was heated from 20 to 600 °C (heating
rate 10 °C min-1).26 Scanning electron microscopy (SEM)
analysis was done on a TESCAN VEGA3 SB microscope.
Elemental analysis was recorded on a Thermo Scientific
Flash 2000 CHN S-O with thermal conductivity detector.
Tetra(p-hydroxyphenyl)resorcarene (4)
It was obtained as purple solid in yield 87%; mp> 250 °C
decomposition; FTIR (KBr) n / cm-1 3380 (O–H), 1176
1
(C–O); H NMR (400 MHz, DMSO-d6) d 5.39-5.50 (s,
4H, ArCH), 5.84-6.57 (m, 24H, ArH), 8.29-8.40 (s, 8OH,
ArOH), 8.61-8.80 (s, 4OH, ArOH), see Figures S2 and S3
in Supplementary Information (SI) section.
Copolymer preparation
The monomer inhibitor (hydroquinone monomethyl
ether, MEHQ) was removed before performing the
polymerization reaction, using a silica gel column. A
mixture of GMA (1.35 mL, 10.20 mmol), MMA (0.45 mL,
4.20 mmol), EDMA (1.20 mL, 6.36 mmol), 1,1-azobis(cyclo
hexanecarbonitrile) (33.9 mg, 0.15 mmol), and cyclohexanol
(4.50 mL, 42.60 mmol) was prepared and then was incubated
at 57 °C for 24 h. Next, the resulting polymer was cooled to
room temperature, cyclohexanol was removed by washing
with absolute ethanol, and the polymer was dried under
reduced pressure.30,31 Poly(GMA-co-EDMA-co-MMA) was
obtained as a white compact solid. FTIR (ATR) n / cm-1 2988,
2947 (C–H), 1723 (C=O), 1147 (C–O).
Synthesis of resorcarenes
The synthesis of these macrocycles was performed by
the reaction between resorcinol and different aldehydes
under acidic conditions, as previously described by
Maldonado and co-workers.27-29
The aldehydes used were butanal, pentanal, hexanal
and p-hydroxybenzaldehyde. To a resorcinol solution
(0.10 mol) and aldehyde (0.10 mol) in ethanol:water (1:1)
(14 mL) it was added dropwise hydrochloric acid (10 mL)
and was reacted at reflux with constant stirring for 1-6 h.
The reaction mixture was cooled in an ice bath and the

Vol. 29, No. 9, 2018
Castillo-Aguirre et al.
1967
Copolymer functionalization
(500 mg) and then the reaction was incubated at 57 °C for
15 h. The resulting solid was cooled to room temperature,
washed with DMF and ethanol absolute, and dried under
reduced pressure. The product was characterized via
ATR-FTIR and Raman spectroscopy.
In basic medium
The functionalization process was adapted from the
methodology proposed by Dan and co-workers.32 Briefly,
a mixture of 1 (0.2 mmol) in N,N-dimethylformamide
(DMF, 3.0 mL) and sodium hydroxide (0.2 mmol) was
added to triturated copolymer poly(GMA-co-EDMA-co-
MMA) (500 mg) and then the reaction was incubated at
57 °C for 15 h. The resulting solid was cooled to room
temperature, washed with DMF and ethanol absolute, and
dried under reduced pressure. For other functionalization
reactions of copolymer poly(GMA-co-EDMA-co-MMA),
the procedure mentioned above was applied, exchanging
the resorcarene 1 for resorcarenes 2, 3 and 4, respectively.
The solid products were characterized via ATR-FTIR and
Raman spectroscopy. After removing the copolymer by
filtration and DMF evaporation, the resorcarene that did
not react was determined gravimetrically.
Results and Discussion
Scheme 1 represents the general procedure for the
formation of resorcarenes 1-4. The synthesis was done
through the acid-catalyzed cyclocondensation of resorcinol
with the respective aldehyde in a mixture of ethyl alcohol
and water (1:1) at 75 °C, in a similar manner to that
described in the literature.33 The products were purified
by means of recrystallization. These derivatives were
characterized using spectral techniques, including FTIR
and 1H NMR (see Experimental section). Compounds had
been previously synthesized by other authors,33-35 and our
spectroscopic data agreed with those reported.
Tetrasodium 2,8,14,20-tetrapropylpentacyclo
[19.3.1.13,7.19,13.115,19]octacosa-1(25),3,5,7(28),9,11,13(27),
15,17,19(26),21,23-dodecaene-4,10,16,22-tetraol-
6,12,18,24-tetrakis(olate) (5) was obtained as a cream-
colored powder at a yield of 45%; mp > 250 °C
decomposition; FTIR (KBr) n / cm-1 3319 (O–H), 1210
(C–O), 1609 (aromatic ring), 2929 (alkyl chains); 1H NMR
(400 MHz, DMSO-d6) d 0.91 (t, 12H, CH3), 1.22 (m,
8H, CH2), 2.15 (q, 8H, CH2), 4.18 (t, 4H, CH), 6.05 (s,
4H, ortho to OH), 7.25 (s, 4H, meta to OH), 9.56 (s, 4H,
OH); 13C NMR (100 MHz, DMSO-d6) d 13.9 (CH3), 20.8
(CH2), 32.6 (CH2), 34.9 (CH), 102.8, 124.0, 132.4, 152.3
(resorcinol ring).
The general scheme of the copolymer synthesis
is illustrated in Scheme 2. Since the composition of
the reaction mixture has a great influence on the final
copolymer structural characteristics, several parameters
concerning the polymerization reaction, such as the amount
of GMA, EDMA, and MMA and the ratio of cyclohexanol,
were optimized. The optimum conditions were as follows:
1.35 mL of GMA, 0.45 mL of MMA, 1.20 mL of EDMA,
33.9 mg of 1,1-azobis(cyclohexanecarbonitrile), and
4.50 mL of cyclohexanol at 57 °C. These conditions were
in agreement with previous reports.24,36 Characterization of
the copolymer was done viaATR-FTIR, thermogravimetric
analysis, and scanning microscopy study.
ATR-FTIR spectrum shows a characteristic signal
corresponding to a C=O bond at 1714 cm-1. In addition,
other characteristic peaks were found at 2930 and 3104 cm-1
due to the C–H stretching vibration, 1449 cm-1 due to
the C–H bending vibration, 1151 cm-1 due to the C–O
stretching vibration of the glycidyl group and 902 cm-1 due
to characteristic epoxy ring absorption. The results showed
that there was an absence of the C=C peak at 1600-1675 cm-1,
In acid medium
In order to determine whether the functionalization
reaction proceeded in acid medium, the procedure proposed
by Dan and co-workers32 was modified, and it was used
H2SO4. A mixture of 4 (0.2 mmol) in DMF (3.0 mL) and
sulfuric acid solution (5% in DMF, 0.25 mL) was added
to triturated copolymer poly(GMA-co-EDMA-co-MMA)
Scheme 1. Synthesis of resorcarenes 1-4.

1968
Surface Modification of Poly(GMA-co-EDMA-co-MMA) with Resorcarenes
J. Braz. Chem. Soc.
Scheme 2. One-pot synthesis of poly(GMA-co-EDMA-co-MMA).
which suggested that the polymerization method was
effective. The thermal stability of the copolymer was
evaluated via thermogravimetric analysis (TGA).According
to Figure 1a, two stages of thermal decomposition were
observed for the copolymer. The first one occurs close to
110 °C, and the second one is a dramatic decomposition
(over 355 °C). These results corroborate the behavior of the
copolymer observed in previous reports.37 So the copolymer
is thermostable below 100 °C and can even be used up to
120 °C for short periods of time in the process of the fixation.
This temperature is suitable, since the reaction is carried
out at 57 °C. GMA-copolymer morphology was analyzed
via SEM imaging (Figures 1b-e). It was observed that the
morphology of the GMA-copolymer is quite uniform, with
continuous pores. The uniform and rich open-pore structure
is suitable for mass transfer efficiency for the reaction
between the oxirane side chain of GMA-copolymer and the
resorcarenes 1-4.
As mentioned above, the presence of an oxirane ring in
GMA-copolymers allows further chemical modifications
Figure 1. Copolymer poly(GMA-co-EDMA-co-MMA). (a) TGA/DSC thermograms. Micrographs at different magnifications: (b) 20 μm, (c) 10 μm,
(d) 5 μm and (e) 2 μm.

Vol. 29, No. 9, 2018
Castillo-Aguirre et al.
1969
Scheme 3. Reaction of poly(GMA-co-EDMA-co-MMA) with resorcarenes.
for various applications. In recent years, research has
been carried out on the attachment of a hydroxyl group
to copolymers of GMA.32,36 For the present research, we
performed the fixation of each resorcarene molecule (1-4)
by its direct reaction with the copolymer’s glycidyl group
in basic media (Scheme 3) and acid media. Modified
copolymers were purified and then characterized using
ATR-FTIR and Raman spectroscopy in the dry state at
room temperature.
The products obtained from the reaction between
poly(GMA-co-EDMA-co-MMA) copolymer and
resorcarenes 1-3 present ATR-FTIR spectra showing a
similar profile compared with the unmodified copolymer,
suggesting that under the used reaction conditions there
is no fixation of these resorcarenes. While, the analysis
of the major peaks observed in the ATR-FTIR spectrum
of modified copolymer using resorcarene 4 (Figure 2,
dotted red line) showed the presence of broad and intense
absorption at 3371 cm-1 corresponding to the O–H groups
of resorcarene rings, the presence of intense peaks at 1651
and 1591 cm-1 corresponding to C=C of aromatic ring and
the peak at 1363 cm-1 attributed to C–O of phenolic residue.
The absorption at 902 cm-1 in unmodified copolymer
spectrum is characteristic of epoxy ring of GMA. The
intensity reduction of this band, in modified copolymer
spectrum, suggests that epoxy ring was opened during the
reaction and this result indicated that resorcinarene 4 was
chemically bound to poly(GMA-co-EDMA-co-MMA). The
ATR-FTIR spectra of the starting copolymer and product
modified with resorcarene 4 are shown in Figure 2.
Figure 2. ATR-FTIR analysis of copolymers. Unmodified (black solid
line), and modified copolymer with resorcarene 4 (red dotted line).
To confirm the results obtained with ATR-FTIR
spectroscopy, the samples were analyzed by Raman
spectroscopy. Products obtained from the reaction between
copolymer and resorcarenes 1-3, in basic media, show a
similar profile compared with the unmodified copolymer
(Figures 3a-d). However, when resorcarene 4 was used,
the modified copolymer Raman spectrum exhibits
different signals compared to the unmodified material;
specifically, absorption at 3057 cm-1 is present. This signal
is characteristic of aromatic systems and confirms that
the resorcarene 4 was the only macrocycle fixed at the
copolymer surface. Our results suggest that the reaction
does not occur with the upper rim hydroxyl groups of the
tested resorcarenes under the above described procedures.
To better understand the results obtained with
resorcarenes 1-3, the reaction between 1 and the copolymer

1970
Surface Modification of Poly(GMA-co-EDMA-co-MMA) with Resorcarenes
J. Braz. Chem. Soc.
tetrasubstituted resorcinol unit (6.05 and 7.25 ppm). For the
proton of hydroxyl group the signal appears at 9.57, but this
signal integrates only for four protons (Figure 4).
13C NMR spectrum of the isolated product (Figure S5,
SI section) shows the signals corresponding to propyl
chains (13.9, 20.8 and 32.6 ppm) and aromatic carbons
(102.8, 124.0, 132.4 and 152.3 ppm). In this way, the
signal at 34.9 ppm confirmed the presence of a methylene
bridge fragment between the aromatic rings. The
information allowed to identify the product as tetrasodium
2,8,14,20-tetrapropyl pentacyclo[19.3.1.13,7.19,13.115,19
]
octacosa-1(25),3,5,7(28),9,11,13(27),15,17,19(26),
21,23-dodecae-ne-4,10,16,22-tetraol-6,12,18,24-
tetrakis(olate) (5). Thus, our results shows that the
modification of poly(GMA-co-EDMA-co-MMA) with
aliphatic resorcarenes does not occur, since the phenolate
is formed, and it is a species that is stabilized by hydrogen
bonding with the hydroxyl group. This phenomenon was
verified when the reactions of copolymer with resorcarenes
2 and 3, in alkaline medium, were carried out, obtaining
also the corresponding tetrasodic salt product. Therefore,
it is necessary to propose the previous functionalization of
the aliphatic resorcarenes for the subsequent modification
of the polymer.
Figure 3. Raman analysis of copolymers. (a) Unmodified, and modified
copolymer with resorcarene (b) 1, (c) 2, (d) 3 and (e) 4.
poly(GMA-co-EDMA-co-MMA) was studied as a model.
After performing the reaction according to the methodology
described above in basic medium, the obtained mixture was
separated by filtration and the solid was washed with DMF
and ethanol. The resulting filtrate was slowly evaporated to
give a solid product, which was analyzed by ATR-FTIR,
1H and 13C NMR. The ATR-FTIR spectrum of the product
showed aromatic ring (1609 cm-1), alkyl chain (2929 cm-1) and
hydroxyl group (3421 cm-1) absorptions. 1H NMR spectrum
displayed characteristic signals of propyl chains (0.91, 1.45,
1.22 and 2.15 ppm), a methylene bridge fragment between
the aromatic rings (4.18 ppm), and aromatic hydrogen of a
Reaction of 4 and the copolymer poly(GMA-co-
EDMA-co-MMA), as mentioned above, allowed the
Figure 4. 1H NMR spectra (400 MHz, DMSO-d6) of compounds 1 and 5.

Vol. 29, No. 9, 2018
Castillo-Aguirre et al.
1971
Figure 5. Conformations of tetra(p-hydroxyphenyl)resorcarene.
fixation of macrocyclic at the surface of the copolymer.
The reaction was carried out using the crude product of 4,
which is a conformational mixture of two isomers (chair
and crown conformers, see Figure 5). To evaluate whether
the two conformational isomers were fixed on the surface
of the copolymer, after separating and washing the modified
copolymer, the filtrate was concentrated to half the volume
with the formation of a solid product, which was isolated
and characterized via 1H NMR. The 1H NMR spectrum of
the product displayed three different hydroxyl moieties at
8.64 ppm, assigned to hydroxyl groups in the lower rim,
and two signals at 8.34 and 8.36 ppm, corresponding to two
classes of hydroxyl groups attached to resorcinol residues in
the macrocyclic system. Careful analysis of all the patterns
confirmed the structure of chair conformer (Figure 5).
According to this analysis, the crown conformer of 4 was
the one fixed on the copolymer surface, maintaining the
selective character of the process previously observed in
solution.25
Figure 6. Raman analysis of modified poly(GMA-co-EDMA-co-MMA)
with 4. (a) Acid media; (b) basic media; (c) unmodified.
were used. The maximum fixation of resorcarene in
the copolymer was 95% when employing two molar
resorcarene excesses per glycidyl residue.
Conclusions
In order to determine if the medium influenced the
modification of the polymer, the reaction was performed
with resorcarene 4 in acidic and basic medium. In both
reactions the oxirane rupture is generated by producing
diol (2,3-dihydroxypropyl methacrylate) or its isomer
(1,3-dihydroxypropyl methacrylate), the latter being a
minor product.38 However, the use of an acid medium
does not allow the deprotonation of the hydroxyl groups
of the lower rim, avoiding the nucleophilic attack of the
resorcarene 4. Both polymers were analyzed by FT-Raman
spectroscopy (Figure 6) and it can be observed, in the
alkaline medium, the signal at 3227 cm-1, corresponding to
aromatic systems, and at 1259 cm-1, corresponding to ether.
Finally, once the best conditions for the fixation of 4
were established, the optimum quantity of resorcarene
required to modify 1 g of copolymer was evaluated. The
amount of modified copolymer was calculated using the
residual resorcarene determined gravimetrically, as it was
mentioned above. For functionalization reaction, different
molar ratios between epoxy group and resorcarene 4
A copolymer with three components, GMA, MMA, and
EDMApoly(GMA-co-EDMA-co-MMA),wasproducedand
characterized via thermogravimetric analysis (TGA/DSC),
scanning electron microscopy (SEM), and ATR-FTIR
spectroscopy. The copolymer was treated under
basic conditions with different macrocyclic systems,
specifically tetrapropylresorcarene, tetrabutylresorcarene,
tetrapentylresorcarene and tetra(p-hydroxyphenyl)
resorcarene. ATR-FTIR and Raman spectroscopy results
showed that only tetra(p-hydroxyphenyl)resorcarene was
covalently bonded to the copolymer, indicating that the
reaction is selective towards the hydroxyl groups of the
lower rim of tetra(p-hydroxyphenyl)resorcarene, while
aliphatic resorcarenes produce salt. The results observed
for the reaction (over the monolithic surface) between the
epoxide ring and the studied resorcarene 4 suggest that
this reaction is regioselective and stereoselective under
described conditions. The reaction was carried out in
acid medium and it was found that modification of the

1972
Surface Modification of Poly(GMA-co-EDMA-co-MMA) with Resorcarenes
J. Braz. Chem. Soc.
polymer with aromatic resorcarene under this condition
does not occur. Finally, it was determined that fixation of
resorcinarens could be up to 95%, using two molar excess.
15. Gramage-Doria, R.; Armspach, D.; Matt, D.; Coord. Chem.
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16. Ruderisch, A.; Iwanek, W.; Pfeiffer, J.; Fischer, G.; Albert, K.;
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Supplementary Information
Supplementary data (structure of compounds 4 and
5; 1H and 13C NMR spectra of compound 4 and 13C NMR
spectrum of compound 5) are available free of charge at
http://jbcs.sbq.org.br as PDF file.
18. Vergara-Barberán, M.; Lerma-García, M. J.; Simó-Alfonso, E.
F.; Herrero-Martínez, J. M.; Anal. Chim. Acta 2016, 917, 37.
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Acknowledgments
We gratefully acknowledge the support of Colciencias
(project: 110165843141, contract: FP44842-037-2015) and
the Universidad Nacional de Colombia, Sede Bogotá.Alver
A. Castillo-Aguirre and Betty A. Velásquez-Silva thank
the program Colciencias Doctorado Nacional No. 647 for
financing their PhD studies.
22. Morinaga, H.; Tsuneishi, F.; Taniguchi, S.; Kawakami, G.;
Tetrahedron Lett. 2014, 55, 3768.
23. Lv, Y.; Mei, D.; Pan, X.; Tan, T.; J. Chromatogr. B 2010, 878,
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24. Safa, K. D.; Nasirtabrizi, M. H.; Eur. Polym. J. 2005, 41, 2310.
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Submitted: March 2, 2018
Published online: April 10, 2018
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