Synthesis and preparation of fluorinated polycarbonates enhancing the light absorption of fluorescent nanoparticles

Article abstract of DOI:10.1166/jnn.2013.7652

A new synthetic method for fluorinated polycarbonates without the use of any toxic phosgene gas is presented. The synthesis consists of a monomer synthesis followed by polymerization. The fluorinated polycarbonate (FPC) was confirmed by Fourier transform infrared spectroscopy (FT-IR) and NMR spectroscopy. The refractive index of the polymer was 1.466 determined by an Abbe refractometer. The contact angle measurement of the FPC films showed the hydrophobicity with water contact angle about 112.6°. These films of varying thicknesses had over 98% transmittance. Taking advantage of the hydrophobicity and high transmittance of the FPCs, nanoparticles of FPCs were prepared directly in an aqueous solution with a reprecipitation method. Combining FPC solution with a solution containing fluorescent polymer (DTMSPV), nanoparticles with a core-shell structure were obtained easily with the reprecipitation method. The fluorescence intensity of the DTMSPV in the core-shell nanoparticles were much enhanced up to 34.1% compared to the molecularly dispersed DTMSPV solution.

Full text of DOI:10.1166/jnn.2013.7652

Copyright © 2013 American Scientific Publishers
All rights reserved
Printed in the United States of America
Journal of
Nanoscience and Nanotechnology
Vol. 13, 6130–6135, 2013
Synthesis and Preparation of Fluorinated
Polycarbonates Enhancing the Light
Absorption of Fluorescent Nanoparticles
Teahoon Park, Syed Nawazish Ali, Jungmok You,
Byeonggwan Kim, and Eunkyoung Kim∗
Active Polymer Center for Pattern Integration, Department of Chemical and Biomolecular Engineering,
Yonsei University, 50 Yonsei-ro, Seodaemun-gu, Seoul 120-749, South Korea
A new synthetic method for fluorinated polycarbonates without the use of any toxic phosgene gas
is presented. The synthesis consists of a monomer synthesis followed by polymerization. The fluo-
rinated polycarbonate (FPC) was confirmed by Fourier transform infrared spectroscopy (FT-IR) and
NMR spectroscopy. The refractive index of the polymer was 1.466 determined by an Abbe refrac-
tometer. The contact angle measurement of the FPC films showed the hydrophobicity with water
contact angle about 112.6ꢀ. These films of varying thicknesses had over 98% transmittance. Taking
advantage of the hydrophobicity and high transmittance of the FPCs, nanoparticles of FPCs were
prepared directly in an aqueous solution with a reprecipitation method. Combining FPC solution
with a solution containing fluorescent polymer (DTMSPV), nanoparticles with a core–shell structure
were obtained easily with the reprecipitation method. The fluorescence intensity of the DTMSPV
Delivered by Publishing Technology to: Florida State University, College of Medicine
in the core–shell nanoparticles were much enhanced up to 34.1% compared to the molecularly
IP: 184.99.174.178 On: Fri, 06 Nov 2015 06:22:32
dispersed DTMSPV solution.
Copyright: American Scientific Publishers
Keywords: Fluorinated Polycarbonate, Enhanced Fluorescence, Core–Shell Nanoparticle,
Reprecipitation Method.
1. INTRODUCTION
low transparency that arises from the high surface energy
and crystalline properties of the fluorine compounds,
which have limited their use in industrial applications.11
Recently, novel fluorinated polymers were synthesized
by combining a fluorinated group and other functional
groups such as urethane12 to overcome some of these
shortcomings as well as to achieve some of the desired
functionalities.
In our previous studies, we reported that photopoly-
merizable perfluorinated methacrylates have a polar
functional carbonate (–O–C( O)–O–), which showed
improved optical and adhesion properties for optical
waveguide materials.2ꢀ5ꢀ13–15 The adhesion of perfluori-
nated methacrylate onto such substrates as glasses and
silicon wafers was enhanced by the introduction of a car-
bonate, a polar functional group.
Fluorinated polymers have attracted much attention due
to their use in a vast variety of applications, such as
optical communication systems, optical filters, and anti-
reflection films used in displays and coatings, but mainly
because of their low optical loss and high resistance.1–5
It is well known that increasing the fluorine content of
a polymer enhances their unique characteristics.6–9 Per-
fluoropolymers, which contain mainly C F bonds, have
excellent chemical and weather resistance. The small
dipole moment of these compounds also contributes to
their oil and water-repellency as well as their low sur-
face tension, low friction coefficient and reduced adhe-
sion to surfaces.10 Therefore, fluorinated polycarbonates
could be an ideal media or encapsulant for active organic
molecules.
Herein, we report the synthesis of a new fluorinated
polycarbonate (FPC) by direct polymerization without
phosgene gas to fabricate a FPC with high transparency,
hydrophobicity and good film properties. In addition, we
report in this study the formation of FPC nanoparticles
However, most of the fluorinated polymers have severe
shortcomings including poor adhesion to substrates and
∗Author to whom correspondence should be addressed.
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1533-4880/2013/13/6130/006
doi:10.1166/jnn.2013.7652

Park et al.
Synthesis and Preparation of Fluorinated Polycarbonates Enhancing the Light Absorption of Fluorescent Nanoparticles
and core–shell FPC nanoparticles containing fluorescent
polymers which can be used for many applications.16ꢀ17
stirred vigorously and refluxed at 50 ꢀC for 65 hours. After
cooling the reaction mixture to room temperature, fresh
CH2Cl2 (30 mL) was added to the reaction mixture. The
mixture was then centrifuged, and the solids were filtered
off and then the mixture washed with a saturated solution
of sodium bicarbonate (40 mL). The organic phase was
then washed with deionized water (30 mL × 2), a satu-
rated solution of sodium bicarbonate (30 mL×3) and then
finally washed again with deionized water (30 mL × 3).
The solution was then dried with anhydrous MgSO4. After
filtrating off the solids, the solvent was removed in vacuo
to afford oily products, which were reprecipitated from a
mixture of CH2Cl2 (∼ 3 mL) and methanol (250 mL) to
yield 1.75 g of product (yield = 86%) as a white solid.
1H NMR (300 MHz, ppm, CDCl3ꢁ; ꢂ 4.62 (4H,
CH2CF2ꢁ, ꢂ 5.20 (s, 4H, CH2Ar), ꢂ 7.37 (s, 4H, CH–
Ar); 19F NMR (282.78 MHz, ppm, CDCl3ꢁ: ꢂ-125.6,
ꢂ-120.0; 13C NMR (75 MHz, ppm, CDCl3ꢁ; ꢂ 155.0
(C O), ꢂ 136.0 (∗C–CH2–O), ꢂ 128.7 (ArCH-∗C–CH2–
O), ꢂ 114.3 (CF2, weak signal), ꢂ 112.1 (CF2, weak signal),
ꢂ 70.27 (∗C–CH2–O), ꢂ 62.9 (CH2–O).
2. EXPERIMENTAL DETAILS
2.1. Materials
Fluorinated diol, 1H,1H,6H,6H-perfluoro-1,6-hexanediol,
and fluorinated tetra ethylene glycol were purchased from
Exfluor Research Corporation, USA. Pyridine, 18-crown-
6, 1,1ꢁ-carbonyl diimidazole, 4-nitrophenyl chloroformate,
and 1,4-benzenedimethanol were purchased from Aldrich
chemicals. Other solvents such as tetrahydrofuran (THF)
and dichloromethane (MC) for the synthesis were prepared
from Aldrich chemicals and used after distillation.
2.2. Synthesis of FPC Monomers
A solution of 4-nitrophenyl chloroformate (6.44 g,
32.0 mmol) in anhydrous dichloromethane (40 mL)
was added dropwise with a 100 mL dropping funnel
into a solution of 1H,1H,6H,6H-perfluoro-1,6-hexanediol
(4.22 g, 16.0 mmol) in anhydrous pyridine (2.53 g,
32.0 mmol) and anhydrous dichloromethane (30 mL) in
a 250 mL round-bottom flask. The mixture was allowed
to stir gently at room temperature for 18 hours. Then,
anhydrous dichloromethane (40 mL) was added and the
2.4. Preparation of FPC Nanoparticles and FPC
Coated Fluorescent Polymer Nanoparticles
Using a 1 wt% solution of FPC in a mixture of chlo-
roform and dichloromethane (9:1), polymer films having
different thickness from 100 to 500 nm were prepared by
spin coating at 1000∼3000 rpm for 30 s. The films were
then annealed at 70 C for 30 min. These polymer films
were used for spectroscopic measurements to confirm the
transmittance and contact angle measurements.
FPC nanoparticles were prepared following the repre-
cipitation method.18 The concentration of FPC in THF
was varied from 0.25 mg/mL to 1 mg/mL to obtain the
optimum size distribution. The FPC solution (100 ꢃL) was
then injected into a 5 mL fluorescent polymer aqueous
solution under sonication. The water-soluble triazine-
bridged copolymer, poly[(diphenylamino-s-triazine)-co-
(2-methoxy-5-propyloxysulfonate-1,4-phenylenevinylene)]
(DTMSPV) was used as a fluorescent polymer which had
been studied in our previous report.19 The solution was
then heated in a microwave oven to remove the organic
solvent and promote the formation of DTMSPV/FPC
nanoparticles. All solution samples were then cooled to
room temperature before characterization.
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reaction mixture was stirred for another 6 hours. The
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reaction mixture was then quenched by adding deionized
Copyright: American Scientific Publishers ꢀ
water (30 mL). The solution was then washed with deion-
ized water (25 mL × 2), followed by a 5.0% solution of
acetic acid (50 mL×3) and then finally washed again with
deionized water (50 mL×2). The solution was dried with
anhydrous MgSO4 and the solids were filtered off. The
solvent and volatile impurities were removed with a rotary
evaporator. The resulting product was recrystallized from
methanol (30 mL) to afford a white crystalline solid prod-
uct with good yield (9.1 g, 95.4%).
1H NMR (300 MHz, ppm, CDCl3ꢁ; ꢂ 8.31 (d, 4H,
ArCH–ꢁC–NO2ꢁ, ꢂ 7.40 (d, 4H, ArCH–ꢁC–O), ꢂ 4.78
(t, 4H, CF2CH2O); 19F NMR (282.78 MHz, ppm, CDCl3ꢁ;
ꢂ-123.5, ꢂ-119.4; 13C NMR (75 MHz, ppm, CDCl3ꢁ;
ꢂ 155.0 (C O), ꢂ 151.7 (∗C O), ꢂ 145.9 (ꢁC–NO2ꢁ, ꢂ
125.5 (ArCH–ꢁC–NO2ꢁ, ꢂ 121.6 (ArCH–∗C–O), ꢂ 114.3
(CF2, weak signal), ꢂ 111.5 (CF2, weak signal), ꢂ 63.7
(CH2–O).
2.3. Synthesis of FPC
2.5. Characterization
In a 250 mL round-bottom flask, 1,4-benzenedimethanol
(0.7 g, 5.06 mmol), bis-nitrophenylcarbonate of fluorinated
diol (3 g, 5.06 mmol), 18-crown-6 (0.31 g, 1.18 mmol)
and anhydrous potassium carbonate (3.5 g) were mixed.
This reaction flask was flushed with argon and was sub-
jected to five vacuum-argon cycles, and then anhydrous
CH2Cl2 (40 mL) was added. The reaction mixture was
UV-visible absorption and transmittance spectra were
measured with a UV-vis-NIR spectrometer (PerkinElmer,
Lambda 750, USA). Fourier transform infrared spec-
troscopy (FT-IR) spectra were obtained using a TENSOR
37 (Bruker). The fluorescence spectra were obtained with
a luminescence spectrometer (Perkin Elmer, Model LS55)
under excitation at 370 nm. 1H NMR analysis was
J. Nanosci. Nanotechnol. 13, 6130–6135, 2013
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Synthesis and Preparation of Fluorinated Polycarbonates Enhancing the Light Absorption of Fluorescent Nanoparticles
(a)
Park et al.
conducted in a BRUKER DPX 300 MHz spectrome-
ter. Chloroform-d (CDCl3ꢁ was used as the solvent, and
tetramethylsilane (TMS) was used as the internal stan-
dard. The average molecular weight of the polymer was
characterized by gel permeation chromatography (GPC)
(model: Waters R-401 ALC/GPC) with THF as the eluent
and polystyrene was used as the standard for calibration.
The thickness of the polymer films was determined using
an Alpha-step profilometer (Tencor Instruments, Alpha-
step IQ) with an accuracy of 1 nm. The surface wettabil-
ity was investigated by distilled water (DI) drop contact
angle measurements using a contact angle meter-CAM 101
model (KSV Instruments Ltd., Finland). More than five
readings were obtained for each sample; the average value
is reported. Weight loss measurements under controlled
heating were carried out with a thermogravimetric anal-
ysis instrument TGA 2050 (TA instrument). It was used
to determine the thermal decomposition temperature of
the fluorinated polymers. Scanning electron microscopy
(SEM) images were obtained with a field emission scan-
ning electron microscope (FE-SEM) system JEOL-6701F.
Transmission electron microscopy (TEM) JEM-2010 was
used to make sure the formation of core–shell nanoparti-
cles. The zeta potential of the nanoparticles was investi-
gated with the ZEN 2001 (Malvern Instruments).
(b)
Fig. 2. (a) FT-IR spectra of (I) the monomer and (II) polymer (FPC),
and (b) 1H NMR spectrum of FPC.
1
spectra. The H NMR spectrum shown in Figure 2(b) also
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confirmed the polymerization.
3. RESULTS AND DISCUSSION
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The thermogravimetric analysis (TGA) curve of FPC is
Copyright: American Scientific Publishers
shown in Figure 3. The mass loss of FPC began at 341 ꢀC.
3.1. Synthesis and Characterization of FPC
This temperature is over 50 ꢀC higher than the degradation
starting temperature of the fluorine-free polymers which
are similar in structure to FPC.20–22 The thermal degrada-
tion temperature of FPC was similar to that of bisphenol
A polycarbonate. This similarity could be attributed to the
number of benzene ring structures in the repeating units
of the two polymers.
The fluorinated bis-nitrophenylcarbonate (FNPC) mono-
mers were synthesized as described in Figure 1. The
goal of the polymerization was to incorporate a functional
group such as a carbonate as part of the fluorinated poly-
mer. The FPC was synthesized by reacting a diol with
FNPCs in a dry CH2Cl2 solution in the presence of anhy-
drous carbonate and 18-Crown-6 (Fig. 1). resulting in an
86% yield as a white solid.20 The weight average molecu-
lar weight (Mw) of FPC was 10,570 with a polydispersity
index (PDI) of 1.32. The fluorine content in the poly-
mer was 34%. Figure 2(a) shows the FT-IR spectra of
the FNPC (monomer) and FPC. The polymerization of
the FNPC monomers was confirmed by the disappearance
of the NO2 peaks at 1350 and 1540 cm−1 in the FT-IR
The refractive index of FPC was lower compared to
normal polycarbonates containing C H bonds, due to
the presence of fluorine in FPC.23ꢀ24 Thus the refrac-
tive index of FPC was 1.4665 with a monitoring wave-
length of 589 nm, while that of bisphenol A polycarbonate
was 1.55.25
The contact angles of the FPC films were 112ꢄ6 0ꢄ6ꢀ,
using water to determine the relative wettability of the
Fig. 1. (a) Synthesis of the bis-nitrophenylcarbonate monomer used for the fluorinated polycarbonate synthesis and (b) polymerization to synthesize
fluorinated polycarbonates.
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Park et al.
Synthesis and Preparation of Fluorinated Polycarbonates Enhancing the Light Absorption of Fluorescent Nanoparticles
Fig. 3. Thermogravimetric analysis of FPC conducted at a heating rate
of 10 ꢀC per minute in a nitrogen atmosphere.
Fig. 4. Transmittance of FPC films with different thicknesses. The aver-
age value of the transmittance was calculated for wavelengths between
400 nm to 800 nm.
FPC film surfaces. There was no significant difference as a
function of film thickness from 100 to 500 nm. The surface
of the FPCs was found to have become more hydropho-
bic due to the fluorine substitution. This can be attributed
to the intrinsic low surface energy of fluoropolymers as
observed for polytetrafluoroethylene (PTFE) and perfluo-
roalkoxy (PFA).26
The structures of the FPC coated fluorescent nanoparti-
cles in the inset of Figures 5(c) and (d) show a core–shell
structure. The nanoparticle structure was further exam-
ined by TEM (inset, Fig. 5(d)). A core–shell structure
was clearly shown due to the contrast difference between
FPC and DTMSPV, indicating the bright shell of FPC
with wall thickness of ∼ 20 nm. The presence of FPC at
the shell was further confirmed by the zeta potential data.
The zeta potential of the DTMSPV aqueous solution and
FPC nanoparticle solution were −46.1 mV and −37.0 mV,
respectively. Interestingly the zeta potential of the FPC
Figure 4 shows the transmittance depending on the film
thickness. Usually fluorinated polymers have high crys-
tallinity and thus show poor transmittance.11 However, the
FPC film had a high transparency of 98% in the range
of from 400 to 800 nm and such high transmittance was
maintained in films of up to 500 nm in thickness. Such
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coated DTMSPV nanoparticle solution was the same as
a high transparency ensures the application of FPCs as a
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that of the FPC nanoparticle solution shown in Figure 6(a),
low refractive index film and protective coating layer for
functional materials such as fluorescent polymers.
Copyright: American Scientific Publishers
indicating that the FPC layer formed on the outer surface
of the DTMSPV. Other previous works have also demon-
strated the formation of encapsulated nanoparticles by the
reprecipitation method.27ꢀ28
3.2. Preparation of FPC Nanoparticles and FPC
Coated Fluorescent Polymer Nanoparticles
FPC nanoparticles (FPC NPs) were readily prepared by
following the reprecipitation method.16 Briefly, the FPC
solution in THF was injected into insoluble solvent (water)
under sonication tꢀo afford nanoparticles upon evaporation
of the THF at 65 C. These nanoparticles were confirmed
by FE-SEM images shown in Figure 5(a).
FPC coated fluorescent polymer nanoparticles were sim-
ilarly prepared using FPC solution (100 ꢃL), which was
injected into a 5 mL aqueous solution of fluorescent
triazine-bridged copolymer (DTMSPV) under sonication.
The solution was then heated in a microwave oven to
remove the organic solvent and promote the formation of
DTMSPV/FPC nanoparticles.
In a 5 mL DTMSPV aqueous solution (1ꢄ65×10−5 M),
100 ꢃL of FPC solution dissolved in THF was directly
injected in order to fabricate the fluorescent nanoparticles
coated with FPC. The size of the nanoparticles became
larger than the size of the DTMSPV nanostructures. As
the concentration of the FPC solution increased from
0.25 mg/mL to 1 mg/mL in THF solution, the size of
the core–shell nanoparticles increased as well (Figs. 5(c)
and (d)).
Fig. 5. FE-SEM images of (a) FPC NPs, (b) DTMSPV, and core–shell
nanoparticles fabricated by the injection of different concentrations of
FPC solutions of (c) 0.25 and (d) 1 mg/mL into the DTMSPV aqueous
solution. All images were obtained at the same magnification of 10,000×.
The scale bar represents 1 ꢃm. ((c), Inset) Enlarged FE-SEM image of
the DTMSPV encapsulated by FPC. ((d), Inset) TEM image of encapsu-
lated nanoparticles.
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Synthesis and Preparation of Fluorinated Polycarbonates Enhancing the Light Absorption of Fluorescent Nanoparticles
Park et al.
(a)
serves as a light collector. Since the refractive index of
the FPC is larger than the media, the input light can be
reflected by the neighboring particles that can be reab-
sorbed at the DTMSPV/FPC nanoparticles like a scatter-
ing and pattern effect applied to the light emitting diodes
(LED) and solar cells.29ꢀ30ꢀ31 Since the FPC is highly trans-
parent, the light loss by the FPC layer is small; thus, the
increase in absorption should be more visible to enhance
the fluorescence. Further study on this interesting light har-
vesting by the transparent FPC coating is in progress to
optimize the structure and stability of the nanoparticles
containing functional molecules.
(b)
4. CONCLUSIONS
We studied FPCs and found a new synthesis method that
does not require the use of harmful gas. This synthe-
sis consists of fluorinated monomer synthesis followed by
polymerization. The FPCs were confirmed by FT-IR and
NMR and the molecular weights of the polymers were
obtained by GPC. Polymer films of various thicknesses
could be made with the FPCs. These films of varying
thicknesses had over 98% transmittance. The thermal prop-
erties of the FPCs were also analyzed by TGA, revealing
high thermal stability. A core–shell nanoparticle solution
was obtained in the fluorescent polymer (DTMSPV) solu-
(c)
tion with the reprecipitation method. The nanostructures
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of DTMSPV were encapsulated by the FPCs due to the
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Copyright: American Scientific Publishers
hydrophobicity of the FPCs. The formation of core–shell
nanoparticles was confirmed by FE-SEM, TEM and zeta
potential measurements. The input light can be reflected
from the FPC shell and reabsorbed at the neighboring
core–shell nanoparticles with no significant energy loss
due to the high transmittance of the FPC layer. Therefore,
the light absorption of the DTMSPV inside the transparent
FPC shell was enhanced and emitted high fluorescence.
Fig. 6. (a) The zeta potential of DTMSPV, FPC NP solution and core–
shell NPs. (b) UV-Visible spectra and (c) fluorescent spectra of FPC
nanoparticle solution (dashed line), DTMSPV solution (solid line), and
core–shell NPs solutions prepared with different concentrations of FPC
solution (red: 1 mg/mL, blue: 0.5 mg/mL, green: 0.25 mg/mL). (b), (c)
inset: Photographic images of the solutions are depicted. Starting on the
left with DTMSPV no FPC addition, followed by three solutions of vary-
ing additions of FPC: 0.25, 0.5, 1 mg/mL, respectively, and FPC NPs
solution.
Acknowledgments: We acknowledge the financial sup-
port of the National Research Foundation (NRF) grant
funded by the Korean government (MEST) through the
Active Polymer Center for Pattern Integration (APCPI)
(R11-2007-050-00000-0), the Pioneer Research Center
Program (2011-0001672), and the Converging Research
Center Program (2011K000631).
Importantly, the solution of the DTMSPV/FPC core–
shell nanoparticles showed enhanced absorbance and flu-
orescence compared to the original DTMSPV solution at
the same concentration (Figs. 6(b) and (c)). The FPC NP
aqueous solution, on the other hand, was transparent and
did not show any fluorescence. The fluorescence quantum
yield of the DTMSPV/FPC solution was 31%, which was
similar to that of the DTMSPV solution without FPC coat-
ing. Thus, the enhanced fluorescence must originate from
the increased absorption as indicated in the UV spectra.
The increased absorption could be attributed to the FPC
layer of the DTMSPV/FPC core–shell nanoparticles which
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Received: 24 July 2012. Accepted: 21 January 2013.
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J. Nanosci. Nanotechnol. 13, 6130–6135, 2013
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