A novel poly(p-phenylene) containing alternating poly(perfluorooctylethyl acrylate-co-methyl methacrylate) and polystyrene grafts by combination of atom transfer radical polymerization and Suzuki coupling processes

Article abstract of DOI:10.1002/pola.26320

A poly(p-phenylene) (PP), carrying perfectly alternating, well-defined poly(perfluorooctylethyl acrylate-co-methyl methacrylate) [P(FEA-co-MMA)] and polystyrene (PS) side chain grafts, was synthesized by the combination of atom transfer radical polymerization (ATRP) and Suzuki cross-coupling processes. First, dibromobenzene and diboronic ester functional macromonomers of P(FEA-co-MMA) and PS, respectively, were prepared by ATRP. In the second step, PP with lateral alternating P(FEA-co-MMA) and PS chains was synthesized by a Suzuki coupling reaction in the presence of Pd(PPh₃)₄ catalyst. The wetting behavior of the polymers was studied by measurements of the static contact angle Θ of thin films (200-400 nm thickness) using water and n-hexadecane as wetting liquids. The obtained fluorinated PP showed high static contact angles with both interrogating liquids, exhibiting simultaneously hydrophobic (Θ_w = 111°) and lipophobic (Θ_h = 67°) properties.

Full text of DOI:10.1002/pola.26320

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A Novel Poly(p-phenylene) Containing Alternating
Poly(perfluorooctylethyl acrylate-co-methyl methacrylate) and
Polystyrene Grafts by Combination of Atom Transfer Radical
Polymerization and Suzuki Coupling Processes
Yasemin Yuksel Durmaz,1 Elif L. Sahkulubey,1 Yusuf Yagci,1,2
Elisa Martinelli,3 Giancarlo Galli3
1Department of Chemistry, Istanbul Technical University, Maslak 34469, Istanbul, Turkey
2Faculty of Science, Chemistry Department, King Abdulaziz University, Jeddah, Saudi Arabia
3
ꢀ
Dipartimento di Chimica e Chimica Industriale, Universita di Pisa, 56126 Pisa, Italy
Correspondence to: Y. Yagci (E-mail: yusuf@itu.edu.tr) or G. Galli (E-mail: gallig@dcci.unipi.it)
Received 28 May 2012; accepted 30 July 2012; published online
DOI: 10.1002/pola.26320
ABSTRACT: A poly(p-phenylene) (PP), carrying perfectly alter-
nating, well-defined poly(perfluorooctylethyl acrylate-co-methyl
methacrylate) [P(FEA-co-MMA)] and polystyrene (PS) side
chain grafts, was synthesized by the combination of atom
transfer radical polymerization (ATRP) and Suzuki cross-cou-
pling processes. First, dibromobenzene and diboronic ester
functional macromonomers of P(FEA-co-MMA) and PS, respec-
tively, were prepared by ATRP. In the second step, PP with lat-
eral alternating P(FEA-co-MMA) and PS chains was synthesized
by a Suzuki coupling reaction in the presence of Pd(PPh3)4 cat-
alyst. The wetting behavior of the polymers was studied by
measurements of the static contact angle
y
of thin films
(200ꢀ400 nm thickness) using water and n-hexadecane as wet-
ting liquids. The obtained fluorinated PP showed high static
contact angles with both interrogating liquids, exhibiting
simultaneously hydrophobic (yw ¼ 111ꢁ) and lipophobic (yh
¼
ꢁ
C
V
67 ) properties. 2012 Wiley Periodicals, Inc. J Polym Sci Part
A: Polym Chem 000: 000–000, 2012
KEYWORDS: alternating copolymer; atom transfer radical poly-
merization (ATRP); fluorinated polymer; graft copolymers;
hydrophobic; lipophobic; poly(p-phenylene); polystyrene
INTRODUCTION Conjugated polymers have been widely
studied for application in devices such as light emitting
diodes,1,2 field effect transistors,3,4 solar cells,5,6 solid-state
lasers,7 chemical and biomolecular sensors.8,9 Among them,
poly(p-phenylene)s (PPs) have been extensively studied due
to the excellent mechanical properties and thermo-oxidative
stability. They are some of the potentially most useful poly-
mers for organic conducting materials and organic polymeric
ferromagnets because of their extended planar conjugated p
system, along with high strength and high heat resistance.
Current methodologies for the direct synthesis of various
PPs are primarily based upon nickel10–16 and palladium-
mediated17,18 cross-coupling reactions largely due to their
preservation of regiochemistry and nearly quantitative yields.
Palladium mediated cross-coupling, known as Suzuki-Miyura
coupling reaction,19 has become a common synthetic way for
formation of carbon–carbon bond because of mild reaction
conditions, high functional groups tolerance, stability, easy to
handling, and low toxicity of organoboron coupling patterns.
Although both catalysts have been widely used, nickel has a
growing interest as more available, economical and environ-
mental friendly catalyst.20 Percec et al. have reported several
examples using nickel catalyst for the preparation of alter-
nating PPs via the homocoupling of readily available phenol
derivatives with high reaction yield.21–25
The solubility problem of PPs in many organic solvents causes
limited processability. Therefore, attachment of conformation-
ally mobile alkyl side chains to the backbone has been usually
applied strategy for the controlled synthesis of soluble and
processable PPs with high molecular weight.26–29 Besides,
incorporation of fluorinated alkyl groups into PPs significantly
increases reaction yield by increasing solubility.30 In addition
to a series of functionalized PPs with pendant alkyl groups,
the synthesis of PP graft copolymers31 by using the macromo-
nomer technique via controlled polymerizations, such as atom
transfer radical polymerization (ATRP)32–35 or ring opening
polymerization (ROP),36–40 was reported.
Polymers containing a pendant perfluoroalkyl group have
unique properties41 such as low friction coefficient, low
C
V
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surface energy, hydrophobicity, self-organization, chemical
inertness, and thermal resistance. They have been explored
in the field of electronics due to low dielectric properties
and have also attracted much attention as optical materials
because of low refractive index and high transmittance.42–44
Incorporation of fluorine and perfluorocarbon units into
polymers has normally been achieved by polymerizations of
fluorine-containing monomers.45–50 Alternatively, fluorine
atoms can be incorporated into preformed polymers by post-
modification through functional groups by using various
organic reactions.51 Recently, many copolymerizations of flu-
orine-containing (metha)acrylates with nonfluorinated acryl-
ates using controlled polymerization methods, including
ATRP,48,52–54 have been reported.
water and than dried over MgSO4. The solvent was removed
by rotary evaporator. The product was purified by passing
through a silica gel column using diethyl ether as eluent.
Finally, the product was obtained as white crystals after
recrystallizing twice from petroleum ether. Yield: 38%, m.p:
89ꢁC. 1H NMR (CDCI3): 4.51 (s, 2H, CH2Br), 7.25 (1H,
aromatic), 7.35 (1H, aromatic), 7.58 (1H, aromatic).
IR (cmꢀ1): 3053–2950 (aromatic and aliphatic CH stretch-
ing), 1488–1455 (aromatic C¼¼C stretching), 1380, 1270–951
(CAH bending), 885, 876, 815, 719, 616.
Synthesis of Benzene-2-methyl-1,4-bis(boronic acid)
2,5-Dibromotoluene (21.74 g, 87 mmol) was dissolved in
140 mL of n-hexane and refluxed for 2 h under nitrogen.
The solution was allowed to cool down to room temperature
for 30 min. The reaction mixture was then cooled to ꢀ78ꢁC,
and n-BuLi (96 mL, 238 mmol) was added at that tempera-
ture. The solution was stirred for an additional 1 h at
ꢀ80ꢁC, and then was allowed to reach slowly to room tem-
perature in 3 h. After stirring at room temperature for 12 h,
the solution was heated to reflux temperature under nitro-
gen for 2 h. The solution was cooled down one more time to
room temperature for 30 min and then to ꢀ78ꢁC, followed
by adding trimethylborate (100 mL, 870 mmol). The solution
was allowed to warm up to room temperature for 3 h before
the reaction was quenched with the addition of 2M HCl. The
two phases were separated, and the water phase was
extracted with four portions of diethyl ether and then dried
over MgSO4 and evaporated to yield the boronic acid as a
white solid, which was used without further purification.
Yield: 50%.
The combination of unique characteristics of fluorine and
specific properties of conjugated polymers can also lead to
the development of new fluorinated conducting poly-
mers55,56 exhibiting superior performance because of their
enhanced chemical environment stability in addition to their
existing intrinsic electronic and optical properties.
Herein, we describe synthesis of a novel PP copolymer, con-
sisting of poly(perfluorooctylethyl acrylate-co-methyl methac-
rylate) [P(FEA-co-MMA)] and polystyrene (PS) alternating
side chain grafts by the Suzuki polycondensation reaction of
the respective aryl diboronic acid diester and aryl dihalide
macromonomers. It was expected that chemical incompatibil-
ity of the fluorocarbon polymer grafts with both hydrocar-
bon polymer grafts and main chain backbone could result in
a microphase separated system. The soluble luminescent
polymer could also be processed to form nonwetting low
surface tension films.
1H NMR (CDCI3): 2.29 (3H, CH3), 7.38 (1H, aromatic), 7.56
(1H, aromatic), 7.73 (1H, aromatic) 7.90 (bs, 4H, OH).
EXPERIMENTAL
IR (cmꢀ1): 3202 (OH stretching of B(OH)2 as a broad peak
overlap with stretching of aromatic CH), 2980 (aliphatic CH),
1488 (aromatic C¼¼C stretching), 1446 (vibration of Ph-B
bond), 1388 (stretching of BAO in B(OH)2), 1321 and 1110
(vibration of the bond BAO and BAOH), 1023, 699.
Materials
Perfluorooctyletyl acrylate (FEA, 97% Fluorochem), (MMA,
99%, Aldrich), Styrene (S, 99%, Aldrich) was passed through
basic alumina column to remove the inhibitor. 2,5-Dibromo-
toluene (98%, Aldrich), N-bromosuccinimide (NBS, 99 %,
Merck), n-butyl lithium (n-BuLi, 2.5M solution in hexane,
Acros), trimethylborate (ꢂ99%, Merck), 1,3-propanediol
(ꢂ99 %, Fluka), NaHCO3 (Aldrich), Pd(PPh3)4 (Merck), ben-
zoyl peroxide (Aldrich), CuBr (98%, Acros), 2,2-bipyridine
(bpy, ꢂ99% Acros), and silicagel 90 (Fluka, 0.2–0.5 mm)
were used as received. CCl4 was distilled over phosphorus
pentoxide, and stored over 4 Å molecular sieves. Hexane was
distilled over sodium wire. Tetrahydrofuran (THF) was dried
over potassium hydroxide, distilled over sodium wire, and
then distilled over benzophenone.
Synthesis of Benzene-2-methyl-1,4-bis(boronic acid)
1,3-propanediol Diester
1,3-Propanediol (10.5 mL, 146 mmol) and 10.85 g benzene-
2-methyl-1,4-bis(boronic acid) were refluxed in dry benzene
(200 mL) for 6 h under nitrogen using a Dean-Stark trap.
The reaction mixture was washed several times with water
and then dried over MgSO4. The solvent was removed in
vacuo to afford a light yellow solid that was recrystallized
from hexane. Yield: 18%. m.p.: 116ꢁC.
1H NMR (CDCI3): 1.99–2.08 (t, 4H, OACH2ACH2ACH2AO),
4.13–4.17 (t, 8H, OACH2ACH2ACH2AO), 2.37 (s, 3H, CH3),
7.50 (s, 1H, aromatic), 7.65 and 7.68 (2H, aromatic).
Synthesis of 1,4-Dibromo-2-(bromomethyl)benzene (1)
2,5-Dibromotoluene, (5.0 g, 20 mmol), NBS (3.91 g, 22
mmol), and benzoyl peroxide (0.096 g, 0.40 mmol) were
heated under reflux in 20 mL of CCl4 under nitrogen for 4 h.
The reaction mixture was filtered to remove succinimide.
Succinimide was washed with a supplementary amount of
CCl4 and finally with a little quantity of CH2Cl2. The com-
bined organic solutions were washed several times with
IR (cmꢀ1): 3053–3019 (aromatic CH stretching), 2955–2926
(aliphatic ACH stretching), 1483 (aromatic C¼¼C stretching),
1421 (vibration of Ph-B bond), 1392, 1372 (BAO in
B(OCH2)2), 1297, 1198, 1157, 1128, 1113 (CAO stretching),
1033, 1005, 925, 903, 724, 688.
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Synthesis of Benzene-2-bromomethyl-1,4-bis(boronic
acid) propanediol Diester (2)
the reaction mixture was degassed by three freeze-pump-
thaw cycles and left in vacuo. The tube was placed at 90ꢁC
in an oil bath and stirred for 90 min. Then the mixture was
diluted with THF, and passed through an alumina column to
remove the copper catalyst. Precipitation of the polymer was
performed in a 10-fold volume of heptane. The solid was
Benzene-2-bromomethyl-1,4-bis(boronic acid) propanediol
diester was synthesized according to a modified literature
procedure.57 Benzene-2-methyl-1,4-bis(boronic acid) pro-
panediol diester (1.79 g, 6.9 mmol), NBS (1.48 g, 8.3 mmol),
and benzoyl peroxide (0.033 g, 0.14 mmol) were heated at
reflux in 15 mL of CCl4 under nitrogen for 24 h. The reaction
mixture was filtered to remove succinimide and washed with
little amount of CCl4 and CH2Cl2. The combined organic solu-
tions were washed several times with water and then dried
over MgSO4. The solvent was removed by rotary evaporator.
The product was purified by passing through a silica gel col-
umn using diethyl ether as eluent. Finally, the product was
obtained as white crystals after recrystallizing twice from
diethyl ether. Yield: 30%.
then collected after filtration (16%, Mn,
¼ 21,640, Mn,
NMR
¼ 18,200, Mw/Mn ¼ 1.49).
GPC
1H NMR (CDCI3): 0.8–2.2 (backbone protons), 2.47 (COOA
CH2ACH2ACF2), 3.57 (COOCH3), 4.26 (bs, COOACH2ACH2A
CF2), 6.92–7.33 (aromatic protons).
IR (cmꢀ1): 2997, 2943 (aromatic and aliphatic CH stretch-
ing), 1727 (C¼¼O stretching), 1477, 1450, 1435, (aromatic
C¼¼C stretching), 1236–1144 (C–F vibration), 653 (CF2
wagging).
1H NMR (CDCI3): 2.02–2.10 (m, 4H, OACH2ACH2ACH2AO),
4.12–4.20 (m, 8H, OACH2ACH2ACH2AO), 4.89 (s, 2H,
ACH2ABr), 7.51 (bs, 1H aromatic), 7.64 (1H aromatic), 7.73
(1H aromatic).
Synthesis of Poly(p-phenylene) by Suzuki
Polycondensation Reaction
A round-bottom-flask equipped with a condenser, a septum
nitrogen inlet–outlet, and magnetic stirrer, was charged with
20 mL 1M of NaHCO3 and 30 mL THF. The solvents were pre-
viously degassed by bubbling nitrogen over a period of 30
min. The mixture was refluxed under nitrogen for 3 h. A 20
mL three neck round–bottom-flask equipped in the same way
as the previous one was charged under inert atmosphere
with PS macromonomer (0.10 g, 0.012 mmol), P(FEA-co-
MMA) macromonomer (0.26 g, 0.012 mmol) and Pd(PPh3)4
(1.0 mg, 8.64 ꢃ 10ꢀ4 mmol). Three milliliter of the mixture
of solvents was introduced with a syringe through the sep-
tum. The reaction was maintained under vigorous stirring
and with the exclusion of oxygen and light at reflux. After
48 h, supplementary amount (5 mL) of solvent mixture was
added through the septum and stirred additional for 24 h.
The polymer was obtained by precipitation in methanol
(44%, Mn, GPC ¼ 36,000, Mw/Mn ¼ 2.46).
IR (cmꢀ1): 3064 (aromatic CH stretching), 2956–2895 (ali-
phatic CH stretching), 1481(aromatic C¼¼C stretching), 1425
(vibration of Ph-B bond), 1393 (vibration of B-O), 1313–
1150 (stretching of CAO linkages), 1097, 1023, 928, 822,
798, 724, 687, 653.
Preparation of Polystyrene Macromonomer by ATRP
A Schlenk tube was charged with CuBr (0.039 g, 0.28 mmol),
bipyridine (0.13 g, 0.83 mmol), benzene-2-bromomethyl-1,4-
bis(boronic acid) propanediol diester as initiator (0.090 g,
0.28 mmol), and styrene (2.48 g, 23.82 mmol). Three freeze-
pump-thaw cycles were performed and the polymerization
was let to proceed under stirring at 110ꢁC for 50 min. After
the given time, the mixture was diluted with THF and passed
through a neutral alumina column to remove copper com-
plex following by rotary evaporation of THF. The polymer
was precipitated in methanol and the solid was collected af-
ter filtration and dried at room temperature in a vacuum
overnight (32%, Mn, NMR ¼ 8250, Mn, GPC ¼ 9150, Mw/Mn ¼
1.40).
1H NMR (CDCI3): 0.82–1.80 [aliphatic of PS and P(FEA-co-
MMA)], 2.47 [C(O)OACH2ACH2ACF2 of P(FEA-co-MMA)],
3.57 [COOCH3 of P(FEA-co-MMA), 4.26 (COOACH2 of P(FEA-
co-MMA)], 7.20–6.56 (aromatic of PS and PP).
IR (cmꢀ1): 3019, 2918, 2849 (aromatic and aliphatic CH
stretching), 1731 (C¼¼O stretching), 1600, 1488–1435, (aro-
matic C¼¼C stretching), 1236–1146 (C–F vibration), 699 (CF2
wagging).
1H NMR (CDCI3): 1.17–2.26 (aliphatic of PS, OACH2
ACH2ACH2AO, ArACH2), 4.13 (OACH2ACH2ACH2AO), 4.47
(PhCH-Br), 6.47–6.57 (aromatic of PS), 7.04–7.46 (aromatic
of PS).
19F NMR (CDCl3/CF3COOH): d (ppm) ¼ ꢀ6 (3F, CF3), ꢀ38
(2F, CF2CH2), ꢀ45 to ꢀ48 (10F, CF2), ꢀ51 (2F, CF2CF3).
IR (cmꢀ1): 3059–3026 (aromatic CH stretching), 2924–2849
(aliphatic CH stretching), 1944–1601 (out-of-plane CAH de-
formation), 1583, 1493, 1452 (aromatic C¼¼C stretching),
1370, 1262, 1181, 1154, 1070, 1027, 907, 840, 802, 756.
Characterization
1H NMR spectra of 5–10% (w/w) solutions in CDCl3 with
Si(CH3)4 as an internal standard were recorded at room tem-
perature at 250 MHz on a Bruker DPX 250 spectrometer. 19F
NMR spectra were recorded with a Varian Gemini VRX300
spectrometer on CDCl3 using CF3COOH as an internal stand-
ard. Gel permeation chromatography (GPC) measurements
were obtained from a Viscotek GPCmax Autosampler system
consisting of a pump, a Viscotek UV detector and Viscotek a
differential refractive index (RI) detector. Three ViscoGEL
Preparation of Poly(perfluorooctylethyl
acrylate-co-methyl methacrylate) [P(FEA-co-MMA)]
Macromonomer by ATRP
CuBr (0.037 g, 0.26 mmol), bipyridine (0.081 g 0.52 mmol),
1,4-dibromo-2-(bromomethyl)benzene as initiator (0.087 g,
0.26 mmol), (perfluorooctylethyl acrylate (2.53 mL,
8.01mmol), methyl methacrylate (MMA) (2 mL, 18.70 mmol)
and toluene (5 mL) were introduced in a Schlenk tube, and
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GPC columns (G2000HHR, G3000HHR, and G4000HHR), (7.8
mm internal diameter, 300 mm length) were used in series.
The effective molecular weight ranges were 456–42,800,
1050–107,000, and 10,200–2,890,000, respectively. THF was
used as an eluent at flow rate of 1.0 mL minꢀ1 at 30ꢁC. Both
detectors were calibrated with PS standards having narrow
molecular weight distribution. Data were analyzed using Vis-
cotek OmniSEC Omni-01 software. Molecular weights were
calculated with the aid of PP standards. FTIR spectra were
recorded on a Perkin-Elmer FTIR Spectrum One B spectrom-
eter. UV spectra were recorded on a Shimadzu UV-1601 spec-
trometer for 4.84 ꢃ 10ꢀ5 mol Lꢀ1 polymer solutions in
CH2Cl2. Fluorescence measurements were carried out using a
Hitachi F-4500 fluorescence spectrophotometer and the exci-
tation and emission spectra of PP were recorded in CH2Cl2
at room temperature. Emission spectrum was obtained with
a maximum at 351 nm, which was determined from scan-
ning emission spectrum of sample in the spectral range of
270–500 nm by fixing excitation wavelength at 260 nm. Dif-
ferential scanning calorimetry (DSC) was performed on Per-
kin–Elmer Diamond DSC calibrated with indium. Glass transi-
tion temperatures were measured, after a first heating (from
0 to 200ꢁC) and cooling (from 200 to 0ꢁC) cycle. Thermo-
grams were recorded during the second heating cycle (from
0 to 200ꢁC) at 10ꢁC/min under nitrogen flow and the glass
transition temperature (Tg) was determined at the midpoint
between upper and lower intersection of the baseline with
the tangent to the transition step. Static contact angle meas-
urements were carried out with a FTA200 Camtel goniome-
ter using water and n-hexadecane of the highest purity com-
mercially available (>99%) as interrogating liquids. Polymer
films were prepared by spin-coating 3 wt% polymer solu-
tions in CHCl3 on glass slides followed by annealing for 12 h
in a vacuum oven at 120ꢁC.
SCHEME 1 Synthesis of aryl dihalide (1) and aryl diboronic
acid (2) initiators.
AB(OH)2 group gives a broad peak at ꢄ3202 cmꢀ1, which
overlaps with aromatic CH stretching. The vibration of phe-
nyl boronic acid linkage Ph-B gives a strong peak at 1446
cmꢀ1. The absorption bands at 1321 and 1110 cmꢀ1 are
assigned to the vibrations of the bonds BAO and BAOH. Af-
ter the esterification reaction, OH stretching of boronic acid
at 3202 cmꢀ1 completely disappeared, while the vibrations
of PhAB and stretching of BAO were still observed at 1421
and 1392 cmꢀ1, respectively. The structures of intermediates
were also confirmed by 1H NMR analysis. The peak at 7.90
ppm corresponding to boronic acid protons completely dis-
appeared after the ester formation. The spectrum of bis(bor-
onic acid) propanediol diester showed that methylene pro-
tons linked to oxygen and methylene protons in the middle
of the ester structure resonance at 4.17 and 2.08 ppm,
respectively. Bromination of methyl group of benzene-2-
methyl-1,4-bis(boronic acid) propanediol diester was clearly
evidenced by the shifting of the peak corresponding to the
methyl protons from 2.37 to 4.89 ppm.
RESULTS AND DISCUSSION
The subsequent step in the process was the preparation of
macromonomers for the final Suzuki coupling reaction. Thus,
dual-functional initiators, 1 and 2 were used in the ATRP of
the respective monomers. In principle, both initiators can be
used for the preparation of fluorinated and nonfluorinated
segmented macromonomers. For our convenience, we
selected initiator 1 for the preparation of the macromonomer
with fluorinated segment because of its structural simplicity.
The synthesis of PP with well-defined macromolecular side
chains by macromonomer technique has been previously
reported by our group.32,57 The Suzuki coupling of aryl hal-
ides and aryl boronic acid containing macromonomers not
only improves solubility and processability of PP but also
conveniently combines the physico-chemical properties of
different polymers, which can be prepared by controlled rad-
ical polymerization techniques. The overall strategy, as pre-
sented in Scheme 1, is based on the preparation of dual
functional compounds having suitable sites for the initiation
of both ATRP and Suzuki coupling processes. 1,4-Dibromo-2-
(bromomethyl)benzene (1) was synthesized through bromi-
nation of the methyl group of commercially available 2,5-
dibromotoluene with N-bromosuccinimide (NBS). Benzene-2-
bromomethyl-1,4-bis(boronic acid) propanediol diester (2)
was synthesized starting from the same compound by a
three step reaction, which included boronic acid formation
and its reaction with 1,3-propanediol followed by the bromi-
nation with NBS of the benzene-2-methyl-1,4-bis(boronic
acid) 1,3-propanediol diester.35 The FTIR analysis of the bor-
onic acid compound indicates that the OH stretching of
Experimentally, P(FEA-co-MMA) was synthesized as a macro-
monomer via ATRP using compound (1) as an initiator
(Scheme 2). Perfluorooctylethyl acrylate (FEA) was deliber-
ately copolymerized with MMA so as to overcome problems
associated with solubility of the fluoropolymer. Copolymer
structure and composition were investigated using 1H NMR
spectroscopy. The small peaks at 6.92 and 7.33 ppm clearly
indicate the presence of aromatic protons belonging to the
1,4-dibromo-2-(bromomethyl)benzene initiator [Fig. 1(b)].
The signals at 4.26 and 2.47 ppm were attributed to methyl-
ene protons of FEA units. The characteristic methyl protons
of MMA segment were also noted at 3.57 ppm. The mole
fractions of FEA and MMA were calculated from the ratio of
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TABLE 1 Synthesis of Poly(p-phenylene) (PP) with Alternating
Polystyrene (PS) and Poly(perfluorooctylethyl acrylate-co-
methyl methacrylate) [P(FEA-co-MMA)] Side Chains by Suzuki
Polycondensation
b
c
Conversion MnNMR
(%)a
(g/mol)
MnGPC
c
Polymers
P(FEA-co-MMA)d 16
(g/mol)
Mw/Mn
21,640
8,250
18,200
9,150
1.49
1.40
2.46
PSe
PPf
a
32
44
g
–
36,000
Determined gravimetrically.
b
Determined by using the ratio between aromatic protons of initiators
and methylene protons of FEA and aromatic protons of PS,
respectively.
SCHEME 2 Synthesis of poly(perfluorooctylethyl acrylate-co-
methyl methacrylate) [P(FEA-co-MMA)] macromonomer by ATRP.
c
Determined by GPC based on polystyrene standards.
d
Polymerization conditions; [M]0/[CuBr]0/[L]0 ¼ 103/1/2 at 90ꢁC in Tolu-
ene for 90 min. Bipyridine used as ligand. Copolymer composition,
FEA/MMA: 30/70 in feed and FEA/MMA: 23/77 in copolymer. Copolymer
composition calculated by using 1H NMR spectrum.
the peak areas around 4.26 and 3.57 ppm, corresponding to
the two methylene protons of FEA and the methyl protons of
MMA, respectively. FEA was copolymerized with MMA 30/70
e
Polymerization conditions; Bulk, [M]0/[CuBr]0/[L]0 ¼ 86/1/3 at 110ꢁC.
Bipyridine used as a ligand.
f
Suzuki polycondensation was performed using Pd(0) catalyst at 90ꢁC
for 5 days.
g
Not calculated by using 1H NMR spectrum.
mol % feed ratio and copolymer composition was calculated
as FEA/MMA: 23/77, which is enough to have sufficient
amount of perfluorooctyl group while maintaining solubility
of polymer chain. The number average molecular weight of
1
P(FEA-co-MMA) was calculated from H NMR spectrum using
the ratio between aromatic protons of initiators and methyl-
ene protons of FEA units. As can be seen in Table 1, there is
a clear correlation between MnNMR and MnGPC, even though
the polymer exhibits relatively broad polydispersity.
The ATRP of styrene using compound (2) as an initiator pro-
vided the second precursor polymer preserving two boronic
ester functionalities, useful for Suzuki coupling in combina-
tion with P(FEA-co-MMA) based macromonomer (Scheme 3).
Also in this case, there is a good agreement between the mo-
lecular weight values obtained by GPC measurement and cal-
culated from 1H NMR spectrum (Table 1). Furthermore, 1H
NMR spectrum shows the presence of boronic ester struc-
ture at the chain end as specified by the peak at 4.13 ppm
corresponding to methylene protons of boronic ester struc-
tures [Fig. 1(c)]. As can be seen in Table 1, although there is
consistency between MNMR and MGPC values, molecular
weight distributions of both macromonomers are slightly
broad due to the fact that polymerizations start with
FIGURE 1 (a) 1H NMR spectra of poly(p-phenylene) (PP), (b)
poly(perfluorooctylethyl
acrylate-co-methyl
methacrylate)
[P(FEA-co-MMA)] macromonomer, (c) and polystyrene (PS)
SCHEME 3 Synthesis of polystyrene (PS) macromonomer by
macromonomer.
ATRP.
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SCHEME 4 Synthesis of poly(p-phenylene) (PP) with alternating poly(perfluorooctylethyl acrylate-co-methyl methacrylate) [P(FEA-
co-MMA)] and polystyrene (PS) side chains by Suzuki polycondensation reaction.
benzylic halides, which lead to inefficient initiation.58
However, as far as the ultimate aim is concerned, sufficient
control of over the molecular weight and desired functional-
ity for the next Suzuki coupling step were achieved.
Typical GPC profiles of precursors and resulted polymer are
shown in Figure 2. GPC trace of the new polymer is shifted
to higher molecular weights, as compared to the starting
P(FEA-co-MMA) and PS macromonomers. GPC trace of PP
did not show any PS precursor trace indicating its quantita-
tive reaction. The slight shoulders on both sides of the chro-
matogram suggest chain growth in different lengths during
PP formation.
In the final step, P(FEA-co-MMA) and PS based macromono-
mers were reacted via Suzuki polycondensation in the pres-
ence Pd(PPh3)4 as catalyst (Scheme 4). The structure of the
1
obtained fluorinated PP was investigated by H NMR, GPC, UV,
1
fluorescence, and DSC analysis. Figure 1 shows H NMR spec-
Figure 3 shows the FTIR spectra of PS, P(FEA-co-MMA), and
PP containing these two precursors as side chains. In the
spectrum of PS [Fig. 3(a)], aromatic overtone and CAH
stretching of PS as well as BAO peak at 1262 cmꢀ1 are
tra of PP and its precursors. Even if the backbone protons of
PP appear together with the aromatic protons of PS, the spec-
trum shows signal of both macromonomers [Fig. 1(a)].
FIGURE 2 (a) GPC traces of polystyrene (PS) macromonomer, (b)
poly(perfluorooctylethyl acrylate-co-methyl methacrylate) [P(FEA-
co-MMA)] macromonomer, and (c) poly(p-phenylene) (PP).
FIGURE 3 (a) FTIR spectra of polystyrene (PS) macromonomer,
(b) poly(perfluorooctylethyl acrylate-co-methyl methacrylate)
[P(FEA-co-MMA)] macromonomer, and (c) poly(p-phenylene) (PP).
6
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FIGURE 6 (a) DSC traces of poly(perfluorooctylethyl acrylate-
co-methyl methacrylate) [P(FEA-co-MMA)] macromonomer, (b)
polystyrene (PS) macromonomer, and (c) poly(p-phenylene)
(PP).
FIGURE 4 (a) UV spectra of poly(perfluorooctylethyl acrylate-
co-methyl methacrylate) [P(FEA-co-MMA)] macromonomer, (b)
polystyrene (PS) macromonomer, and (c) poly(p-phenylene)
(PP) in CH2Cl2.
P(FEA-co-MMA) and PS macromonomer did not show any
fluorescence properties, PP gave a strong fluorescence emis-
sion. The excitation spectrum of PP presented a maximum at
260 nm, and emission spectrum obtained at this excitation
wavelength had a maximum at 351 nm.
detectable. Characteristic absorption peaks of P(FEA-co-
MMA) at 1727 and 1144 cmꢀ1 corresponding to C¼¼O and
CAF bond, respectively, are clearly observed in the PP spec-
trum at 1731 and 1146 cmꢀ1
.
UV absorption spectra of macromonomers and correspond-
ing PP recorded in CH2CI2 solutions with same concentra-
tions are shown in Figure 4. While P(FEA-co-MMA) macro-
monomer does not show significant absorption, the PS based
macromonomer has intense absorption at around 262 nm
associated with phenyl ring. UV spectrum of PP has a peak
with higher intensity at wavelength close to the absorbance
wavelength of PS macromonomer because of the presence of
supplementary phenylene rings in the main chain. Moreover,
absorption shoulders at 270 and 375 nm further evidence
for the formation of a PP chain.
Also, the thermal behavior was investigated by DSC (Fig. 6).
Glass transition temperatures (Tg) were measured during the
second heating cycle (from 0 to 200ꢁC) at 10ꢁC/min under
nitrogen flow. PS and P(FEA-co-MMA) macromonomers show
the typical glass transitions at 100 and 65ꢁC, respectively. PP
displayed the two transitions at 66 and 104ꢁC indicating
microphase separation of the two side chain grafts from the
backbone. No evidence of a mesophase formation was
detected for P(FEA-co-MMA) and PP. The random incorpora-
tion of 77 mol % of MMA units in the copolymer introduced
constitutional disorder, which impeded formation of a meso-
phase structure typical of the fluorinated homopolymer.44,59
Furthermore, fluorescence properties of PP and macro-
monomers were investigated. As shown in Figure 5, while
The wetting behavior of the polymers was studied by meas-
urements of the static contact angle y of thin films (200ꢀ400
nm thickness) using water and n-hexadecane as wetting
liquids (Table 2). The films were spin-coated onto glass slides,
dried under vacuum overnight, and then annealed for 12 h at
120ꢁC to achieve equilibrium morphologies.
The values of y with water and n-hexadecane are conven-
tionally used to estimate qualitatively hydrophobicity (yw
>
ꢄ90ꢁ) and lipophobicity (yh > ꢄ60ꢁ), respectively. The fluo-
rinated PP and its precursor P(FEA-co-MMA) showed high
static contact angles with both interrogating liquids, exhibit-
ing both hydrophobic (yw ¼ 111ꢁ and 112ꢁ, respectively)
and lipophobic (yh ¼ 67ꢁ and 69ꢁ, respectively) properties.
The dual character is typical of fluorinated polymers, as
opposed to most other polymers, like polyolefins and PPs,
that are hydrophobic, but not lipophobic at the same time
(see PS in Table 2). In fact, PS was completely wetted by
n-hexadecane. On the other hand, dilution of the FEA moi-
eties with PS units in the PP did not affect the self-assembly
process of the pendant perfluorinated chains at the surface.
FIGURE 5 (a) Normalized excitation and (b) emission fluores-
cence spectra of poly(p-phenylene) (PP) in CH2Cl2 at room
temperature.
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TABLE 2 Static Contact Anglesa and Surface Tensionsb of
Poly(p-phenylene) (PP), Poly(perfluorooctylethyl acrylate-co-
methyl methacrylate) [P(FEA-co-MMA)] and Polystyrene (PS)
polymer side chains along the aromatic polymer backbone.
The method pertains to the elegant combination of ATRP
with Suzuki coupling processes. The macromonomers of
P(FEA-co-MMA) and PS were obtained by ATRP and subse-
quently used in Suzuki polycondensation to yield desired PP.
The structures of such complex macromolecules have been
characterized as they showed excellent solubility in common
organic solvents at room temperature. High solubility, fluo-
rescence, and low surface tension properties of the PP graft
copolymer imply that it is a promising material for many
applications where a luminescent PP underlayer is hidden by
a hydrophobic and lipophobic overlayer.
b
db
pb
cS
cS
cS
Film
PP
yw (ꢁ)
yh (ꢁ)
(mN/m)
(mN/m)
(mN/m)
111 6 1
112 6 2
67 6 2
69 6 2
14.1
13.4
13.3
12.7
0.8
0.7
P(FEA-co-
MMA)
PS
90 6 2
ꢄ0
–
–
–
a
Measured with water and n-hexadecane.
Calculated with the Owens–Wendt–Kaelble method: cS is the disper-
b
d
p
sion component, cS is the polar component.
REFERENCES AND NOTES
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tion is known for a variety of fluorinated polymers and can
be exploited in application fields were nonstick, antisoiling,
and anti(bio)fouling properties are required.60–67
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