A unique stepped multifunctionality of perfluorinated aryl compound and its versatile use in synthesizing grafted polymers with controlled structures and topologies

Article abstract of DOI:10.1002/pola.24673

A unique stepped multifunctionality of perfluorinated aryl compound for the first time was studied by using model reactions between 2,5- dipentafluorophenyl-1,3,4-oxadiazole (FPOx) and mono functional p-cresol at different reaction conditions. Four distinctively different levels of reactivity were discovered for the para and ortho C-F of FPOx, which could be easily triggered by the reaction temperature in the range of r.t. to 160 °C. C-F of all levels of reactivity could react quantitatively with nucleophiles (such as phenoxide); and by controlling the reaction conditions, the low-level-reactivity C-F would not interfere with the reaction of C-F of higher reactivity. Application of this multistepped reactivity of FPOx in quantitative postpolymerization functionalization of polymer was successfully demonstrated. Stoichiometric amount of p-cresol, with the molar feed ratio of p-cresol in relative to the repeat unit of the polymer of FPOx and 6F-BPA in the range of 1-4, could be readily grafted onto the polymer by simply controlling the reaction temperature. FPOx-based, versatile one-pot synthesis of high molecular-weight grafted polymers with well-controlled structures and topologies were also demonstrated.

Full text of DOI:10.1002/pola.24673

A Unique Stepped Multifunctionality of Perfluorinated Aryl Compound
and Its Versatile Use in Synthesizing Grafted Polymers with Controlled
Structures and Topologies
ZHENHUA ZHAO, XIAOHUA MA, AIXIN ZHANG, NAIHENG SONG
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education,
College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
Received 16 February 2011; accepted 14 March 2011
DOI: 10.1002/pola.24673
Published online 6 April 2011 in Wiley Online Library (wileyonlinelibrary.com).
ABSTRACT: A unique stepped multifunctionality of perfluori-
nated aryl compound for the first time was studied by using
model reactions between 2,5-dipentafluorophenyl-1,3,4-oxadia-
zole (FPOx) and mono functional p-cresol at different reaction
conditions. Four distinctively different levels of reactivity were
discovered for the para and ortho CAF of FPOx, which could
be easily triggered by the reaction temperature in the range of
r.t. to 160 ꢀC. CAF of all levels of reactivity could react quantita-
tively with nucleophiles (such as phenoxide); and by control-
ling the reaction conditions, the low-level-reactivity CAF would
not interfere with the reaction of CAF of higher reactivity.
Application of this multistepped reactivity of FPOx in quantita-
tive postpolymerization functionalization of polymer was suc-
cessfully demonstrated. Stoichiometric amount of p-cresol,
with the molar feed ratio of p-cresol in relative to the repeat
unit of the polymer of FPOx and 6F-BPA in the range of 1–4,
could be readily grafted onto the polymer by simply control-
ling the reaction temperature. FPOx-based, versatile one-pot
synthesis of high molecular-weight grafted polymers with well-
controlled structures and topologies were also demonstrated.
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2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem
49: 2423–2433, 2011
KEYWORDS: controlled polymer synthesis; functionalization of
polymers; perfluorinated aromatics; polyethers; quantitative
functionalization; stepped multifunctionality; synthesis; topology
INTRODUCTION Postpolymerization functionalization repre-
sents an efficient approach for synthesizing functional
polymers with desired properties.1–4 One critical challenge,
however, has been the quantitative control of functionaliza-
tion and precise tailoring of materials properties. This is
even true when multiple functional groups are to be incorpo-
rated into a polymer hierarchically, uniformly and densely.
Although combination of different coupling chemistries could
be employed to address this challenge,3,4 it involves great
difficulty with synthesizing specific reactive group-containing
polymers and functional molecules. Thus, to enable quantita-
tive hierarchical functionalization, simple solutions for realiz-
ing robust multifunctional polymers having high but non-
crossing reactivity to readily accessible reactive groups (e.g.,
hydroxyl and amine) are desired.
the EWG, for quantitative reactions with nucleophiles.6,7 The
para CAF can have a higher reactivity than the ortho CAF.8,9
On the contrary, an electron-donating substituent (e.g.,
alkoxyl and aryloxy) will deactivate the CAF bond. Given
these, a strong EWG-bearing perfluorinated aryl compound
[e.g., 2,5-dipentafluorophenyl-1,3,4-oxadiazole (FPOx), Fig. 1]
could be expected to exhibit an inherent multifunctionality
with self-regulated stepped reactivity: (1) the para CAF1 has
the highest reactivity and will react predominantly with
nucleophiles;8,9 (2) once the para F1 is substituted with an
aryloxy, the reactivity of ortho CAF (i.e., CAF2 and CAF3)
will decrease, yielding a distinctive difference (or ‘‘step’’) in
reactivity between para and ortho CAF bonds. Due to the
strong activation effect of oxadiazole and the neighboring flu-
orine atoms, the ortho CAF may still undergo quantitative
condensation reaction with nucleophiles at improved reac-
tion conditions; (3) substitution of one of the ortho F (e.g.,
F2) with aryloxy will further depress the reactivity of the
remaining ortho CAF3, giving rise to the second reactivity
step between CAF2 and CAF3 (Fig. 1). Similarly, CAF3 may
remain reactive to nucleophiles at appropriate conditions.
Thus, by optimization and control of reaction conditions,
these three levels of reactivity may be explored for quantita-
tive hierarchical functionalization of polymers. Up to now,
Nucleophilic substitution reactions between aryl CAF and
strong nucleophiles (e.g., phenoxide) have been well docu-
mented and extensively used for synthesizing high molecular
weight (Mw) poly(aryl ether)s.5–7 The reactivity of aryl CAF
is due to the high electron negativity of fluorine and dictated
to a great extent by the electronic property of the aryl struc-
ture. Typically, the presence of an electron-withdrawing
group (EWG, e.g., ketone, sulfone, and cyanide) can effec-
tively activate the para or ortho CAF bond(s), in relative to
Correspondence to: N. Song (E-mail: nsong@pku.edu.cn)
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Journal of Polymer Science Part A: Polymer Chemistry, Vol. 49, 2423–2433 (2011) 2011 Wiley Periodicals, Inc.
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JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
activated the ortho CAF bonds, FPOx reacted efficiently with
four equivalent of p-cresol to give the four substituted 4T-
FPOx at a very high isolation yield of 87%. A reaction with a
molar p-cresol/FPOx (c/f) ratio of about 3 was also carried
ꢀ
out at 60 C, which resulted in a mixture of double, tri- and
four substituted products, suggesting the equivalence of
0
ortho CAF2 and CAF2 in reactivity.
It is interesting to finꢀd that when the reaction temperature
was increased to 110 C, FPOx reacted with only five equiva-
lent amount of p-cresol to give 5T-FPOx. Since the reactivity
0
of CAF3 and CAF3 are not expected to be different, as evi-
denced by the well resolved 1H NMR and 19F NMR (Figs. 2
and 3) spectra of 4T-FPOx, this can be explained by the
steric effect of 5T-FPOx, which limits the accessibility of p-
cresol to the remaining ortho CAF bond. Further increase of
ꢀ
reaction temperature to above 150 C led to the fully substi-
tuted product 6T-PFOx at an isolation yield of 93%.
Figure 2 shows the expanded 1H NMR spectra of the toly-
loxylated FPOx, which agree very well with the expected
structures. It can be seen that with the substitution of para
and ortho CAF by tolyloxy, the aryl protons (e.g., protons 1
and 2) moved step by step to higher fields, indicating an
increasing electron density of the fluorinated phenyl ring. It
is noted that all the reactions between FPOx and p-cresol are
nearly quantitative and lack of side reactions, which are
highly desirable for synthesizing grafted functional polymers.
The degree of reaction could be easily manipulated by con-
trolling the reaction temperature and the molar c/f ratio. For
example, 2T-FPOx can be first prepared by reacting FPOx
with 2 mol equivalence of p-cresol at room temperature, fol-
lowed by reacting additional 3 mol equivalence of p-cresol at
110 ꢀC to yield 5T-FPOx. This makes hierarchical or multi-
step grafting of functional groups possible.
FIGURE 1 Illustration of structure of FPOx and the stepped
reactivity of CAF bonds.
although high Mw polymers based on perfluorinated aro-
matic monomers are known,8–10 the multifunctionality of
stepped reactivity was not yet known. Indeed, the reaction
of ortho CAF with nucleophiles has been purposely
depressed to achieve linear noncrosslinking polymers.
Herein, we report the discovery of the unique ‘‘stepped
multifunctionality’’ of perfluorinated aryl compound and
its versatile use in synthesizing grafted polymers with well-
controlled structures and topologies.
Application of the stepped reactivity of FPOx in quantitative
functionalization of polymer was carried out by first poly-
merizing FPOx with 6F-BPA to give the linear polymer P1
(Mn ¼ 21,000, GPC), followed by grafting with p-cresol in
DMF with the presence of potassium fluoride as the base
(Scheme 2). The feed molar ratio of p-cresol in relative to
the repeat unit of P1 (c/r ratio) was controlled in the range
of 1–4 and the grafting reaction temperature in the range of
60–160 ꢀC depending on the c/r ratio. The syntheses and
properties of the grafted polymers are summarized in Table
1. For all the cases, stoichiometric amount of p-cresol were
RESULTS AND DISCUSSION
To understand the stepped reactivity of perfluorinated aro-
matics, FPOx was chosen as the compound of study because
of the strong activation effect of oxadizaole (Ox),11 which is
known to be capable of facilitating reactions between para
CAF and phenoxide at room temperature.8 It is expected
that Ox will also activate the ortho CAF to react efficiently
with strong nucleophiles at appropriate reaction conditions,
even with the presence of deactivating aryloxy substituent(s).
The synthesis of FPOx has been reported by Ding and
Day,8(a) where FPOx was polymerized with hexafluorobisphe-
nol A (6F-BPA) to yield high Mw linear polymers.
1
grafted onto the polymer, as estimated from H NMR spectra
by comparing the integral of all aryl protons in relative to
the integral of aryl protons of 6F-BPA residue (Fig. 4). As the
grafting density increased, the glass transition temperature
of the grafted polymer decreased (Fig. 5 and Table 1). One-
pot, multistep synthesis of grafted polymers with well-
defined structures is also possible. As shown by Scheme 3
(one-pot route 1), FPOx-based polymer P1 can be subjected
to the stoichiometric grafting right after the polymerization,
without the need of separation and purification of the poly-
mer, by adding p-cresol and increasing the reaction tempera-
ture, as exemplified by the synthesis of P1-a0 and P1-b0.
Scheme 1 shows the model reactions of FPOx with p-cresol
at different temperatures in anhydrous DMF using potassium
fluoride as the base. It was found that when the reaction
was carried out at room temperature (ca. 23 C), FPOx could
react quantitatively with two molar equivalent of p-cresol at
ꢀ
0
the para positions (i.e., CAF1 and CAF1 ) to yield the double
substituted 2T-FPOx. The reaction went to completion within
2 h. Extension of the reaction time (e.g., 3 h) yielded no dis-
cernible amount of further substituted products. Upon
increasing the reaction temperature to about 60 ꢀC, which
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SCHEME 1 Model reactions between FPOx and p-cresol.
ꢀ
By taking advantage of the high reactivity of the ortho CAF
at elevated temperatures, polymerization of 4,40-disubsti-
tuted FPOx (i.e., 2T-FPOx) with 6F-BPA was carried out at 60
ꢀC in DMF in the presence of potassium fluoride as the base
(Scheme 3 and Table 2). As expected, high Mw polymer P2
(Mn ¼ 15,100, GPC) was obtained. In comparison with P1-b
that has the same chemical composition, P2 has a different
topology (Fig. 6). The grafted polymer P1-b has the grafted
functional groups alternatively arranged along a linear chain,
whereas P2 has the two side groups head-to-head linearly
aligned along a somewhat zig-zag backbone. Depending on
the side chain structures, this difference in topology may
lead to different properties of the polymer, such as inter-
chain interaction and thermal properties. Figure 7 shows the
different 1H NMR spectra of P1-b and P2. Similarly, P2 can
also be prepared via a one-pot two-step synthesis (P20, one-
pot route 2 in Scheme 3).
60 C by polymerizing FPOx and 6F-BPA with the presence of
a controlled amount (e.g., 1 or 2 molar equivalence) of mono
functional p-cresol (Scheme 3). Since both para and ortho
ꢀ
CAF bonds are highly reactive at 60 C, an irregularly grafted
polymer P3-a (Mn ¼ 14,500, GPC) and P3-b (Mn ¼ 16,500,
GPC) were obtained. In comparison with P1-b and P2, the
topologically different P3-b (Fig. 6) is expected to exhibit dif-
ferent materials properties. For example, P3-b (Tg ¼ 124 ꢀC)
exhibited a much lower glass transꢀition temperature than P1-
ꢀ
b (Tg ¼ 135 C) and P2 (Tg ¼ 132 C) (Tables 1 and 2).
EXPERIMENTAL
Materials: Hexafluorobisphenol A (6F-BPA, Zhejiang Sanhe
Pharmachem) and p-cresol were purified by recrystallization
from toluene and ligroin, respectively. Anhydrous N,N-dime-
thylformamide (DMF) was distilled over phosphorus penta-
oxide and stored over molecular sieves (3 Å). Anhydrous
potassium fluoride was purchased from Beijing Chemical Re-
agent Company and treated at 200 ꢀC over night.
One-pot one-step syntheses of random-topology P3 (i.e., P3-a
and P3-b) were also carried out at an elevated temperature of
MULTIFUNCTIONALITY OF PERFLUORINATED ARYL COMPOUND, ZHAO ET AL.
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JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
FIGURE 2 Expanded 1H NMR (400 MHz, CDCl3) spectra of p-tolyloxylated FPOx.
Pentafluorobenzoic acid was purchased from Yongtai Chemi-
cal and used as received. All other chemicals and reagents
were purchased from Beijing Chemical Reagent Company
and used as received.
of 1.0 mL/min. All GPC data were calibrated with linear poly-
styrene standards. FTIR spectra were recorded on a Bruker
Vector 22 Fourier transform infrared spectrometer. ESI-mass
spectra were measured on a Bruker Daltonics apex IV FTMS
mass spectrometer. Element analysis was conducted by an Ele-
mentar Vario EL instrument (Elementar Analysensysteme
GmbH). Thermogravimetric analysis (TGA) was performed on a
TA Q600 SDT instrument at a heating rate of 10 ꢀC/min in
nitrogen. Differential Scanning Calorimetry (DSC) was recorded
with a TA Q100 thermal analyzer at a heating rate of 10 ꢀC/
min in nitrogen.
Measurements: Nuclear magnetic resonance (NMR) spectra
were recorded at room temperature on either a Bruker ARX
400 MHz spectrometer (1H NMR 400 MHz and 13C NMR 100
MHz) or a Varian Mercury 300 MHz spectrometer (1H NMR
300 MHz and 13C NMR 75 MHz) using tetramethylsilane as an
internal standard. 19F NMR spectra were recorded on a Varian
300 MHz (19F NMR 282 MHz) using trifluoroacetic acid as an
external standard. The chemical shifts are reported in the ppm
scale. Gel permeation chromatographic (GPC) measurements
were performed with a Waters 510 system at room tempera-
ture. Tetrahydrofuran was used as the eluent with a flow rate
Synthesis of Model Compounds
2,5-Bis(pentafluorophenyl)-1,3,4-oxadiazole (FPOx)
FPOx was prepared according to the literature method (Ding
and Day) and modified as follows:
A
mixture of
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FIGURE 3 19F NMR (282 MHz, CDCl3) spectra of p-tolyloxylated
FPOx.
pentafluorobenzoic acid (5.1 g, 24.0 mmol), hydrazine sulfate
(1.9 g, 14.6 mmol), and polyphosphoric acid (45 g) was
stirred and heated in a 250 mL round-bottomed flask at 150
ꢀC under argon fꢀor 2 h. The temperature was then slowly
increased to 200 C and the mixtureꢀwas heated for another
2 h. After cooling down to about 50 C, the reaction mixture
was poured into vigorously stirring distilled water (200 mL).
The resulting white powdered solid was collected by filtra-
tion and washed with hot water until neutral.
SCHEME 2 Synthesis of FPOx-based linear and grafted
polymers.
2,5-Bis(2,3,5,6-tetrafluoro-4-(p-tolyloxy)phenyl)-1,
3,4-oxadiazole (2T-FPOx)
After drying, the crude product was recrystallized from tolu-
ene/methanol mixture (3/7, v/v) twice to give white needle-
like crystals (3.5 g, 73% yield): mp. 155–156 ꢀC; 13C NMR
A mixture solution of FPOx (3.071 g, 7.637 mmol), p-cresol
(1.801 g, 16.660 mmol) and anhydrous potassium fluoride
(1.902 g, 32.736 mmol) in DMF (30 mL) was prepared and
stirred under argon at room temperature for 2 h. The reac-
tion solution was poured into a mixture solution of methanol
and distilled water (200 mL, 1/1, v/v) and the resulting
powder precipitates was collected by filtration and thor-
oughly washed with methanol and distilled water.
1
(100 MHz, CDCl3): d: 156.2 (m), 145.2 (dm, JF-C ¼ 260 Hz),
1
1
143.6 (dm, JF-C ¼ 261 Hz), 138.0 (dm, JF-C ¼ 252 Hz),
99.8–100.2 (m); 19F NMR (282 MHz, CDCl3): d ꢁ57.0 to
ꢁ57.1 (m, 4F, ArAF meta to Ox), ꢁ67.8 to ꢁ67.9, (m, 2F,
ArAF para to Ox), ꢁ81.1 to ꢁ81.2 (m, 4F, ArAF ortho to
Ox).
TABLE 1 Synthesis and Characterization of p-Cresol Grafted Polymers P1-a–P1-d
Feed
Ratioa
Temp.
(ꢀC)b
Yield
(%)
Grafting
Ratio (%)c
Mn
(ꢂ104)d
Tg
(ꢀC)e
Td
(ꢀC)f
Polym.
PDId
P1
ꢁ
23
90
84
91
85
88
ꢁ
100
100
89
2.1
2.1
2.2
2.1
1.6
2.4
2.6
2.9
2.7
2.6
175
149
135
131
128
478
459
436
432
416
P1-a
P1-b
P1-c
P1-d
a
1:1
2:1
3:1
4:1
60
60
110
160
100
Molar feed ratio of p-cresol versus repeat unit of P1.
Grafting reaction temperature.
b
c
d
e
f
Determined from proton NMR analysis.
Number-average molecular weight (Mn) and polydispersity (PDI) determined by GPC.
Glass transition temperature measured by DSC in nitrogen at a heating rate of 10 ꢀC/min.
Onset temperature for 5% weight loss measured by TGA in nitrogen at a heating rate of 20 ꢀC/min.
MULTIFUNCTIONALITY OF PERFLUORINATED ARYL COMPOUND, ZHAO ET AL.
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JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
1639, 1604, 1494(br), 1410, 1205, 991, 848, 814, 490; Anal.
Cacld. for C42H28F6N2O5: C, 66.84; H, 3.74; N, 3.71; Found: C,
66.32; H, 3.80; N, 3.68; ESI-HRMS (m/z): 755.1978 [MþH]þ.
2-(3,5-Difluoro-2,4,6-tris(p-tolyloxy)phenyl)-
5-(2,3,5-trifluoro-4,6-bis(p-tolyloxy)phenyl)-1,3,
4-oxadiazole (5T-FPOx)
A mixture of FPOx (0.788 g, 1.96 mmol), p-cresol (1.397 g,
12.92 mmol) and anhydrous potassium fluoride (1.14 g, 19.6
ꢀ
mmol) in DMF (14 mL) was prepared and stirred at 110 C
under argon for 7 h. After cooling to room temperature, the
reaction mixture was filtered and the filtrate was rotoevapo-
rated to yield a liquid residue, to which was added methanol
(4 mL) to develop a white crystalline product.
The product was collected by filtration, washed with distilled
water and methanol, and recrystallized from toluene/metha-
nol (15/85, v/v) to give white needle crystals (1.4 g, 85%
yield): mp. 146–147 ꢀC; 1H NMR (400 MHz, CDCl3): d 7.12
(dd, 4H, J ¼ 8.4 Hz, J ¼ 3.5 Hz), 6.97–7.02 (m, 6H), 6.87 (dd,
4H, J ¼ 8.4 Hz, J ¼ 2.1 Hz), 6.75 (d, 4H, J ¼ 8.4 Hz), 6.68 (d,
2H, J ¼ 8.4 Hz), 2.32 (s, 3H), 2.31 (s, 3H), 2.26 (s, 9H); 19F
NMR (282 M, CDCl3): d ꢁ58.7 (dd, 1F, J ¼ 21.7 Hz, J ¼ 10.4
Hz), ꢁ63.7 (s, 2F), ꢁ64.2 (d, 1F, J ¼ 10.4Hz), ꢁ74.0 (d, 1F, J
¼ 21.7Hz); FTIR (KBr, cmꢁ1): 3034, 2919, 1639, 1604, 1497,
1460, 1204, 990, 846, 815, 488; Anal. Calcd. for
FIGURE 4 1H NMR (400 MHz, CDCl3) spectra of P1 and grafted
polymers P1-a, P1-b, P1-c, and P1-d.
ꢀ
After drying at 60 C in an oven over night, the crude prod-
uct was recrystallized from toluene/methanol (3/7, v/v) to
give white needle-like crystals (4.2 g, 96% yield): mp. 155–
156 ꢀC; 1H NMR (400 MHz, CDCl3): d 7.17 (d, 4H, J ¼ 8.4
Hz), 6.95 (d, 4H, J ¼ 8.8 Hz), 2.35 (s, 6H); 13C NMR (100 M,
C
49H35F5N2O6: C, 69.83; H, 4.19; N, 3.32; Found: C, 69.40; H,
4.25; N, 3.27; ESI-HRMS (m/z): 843.2466 [MþH]þ.
5T-FPOx (an Altenative Two-Step Synthesis)
A mixture of 2T-FPOx (0.99 g, 2.46 mmol), p-cresol (0.93 g,
8.59 mmol) and anhydrous potassium fluoride (0.70 g, 12.0
1
CDCl3): d 156.5 (s br), 154.7, 145.4 (dm, JF-C ¼ 260 Hz),
1
141.7 (dm, JF-C ¼ 252 Hz), 137.7–137.9 (m), 130.3, 115.9,
ꢀ
mmol) in DMF (12 mL) was prepared and stirred at 110 C
99.8–100.0 (m), 20.6; 19F NMR (282 M, CDCl3): d ꢁ58.3 to
ꢁ58.4 (m, 2F), ꢁ74.2 to ꢁ74.3 (m, 2F); FTIR (KBr, cmꢁ1):
1651, 1606, 1507 (br), 1215, 1103, 990, 818, 492; Anal.
Calcd. for C28H14F8N2O3: C, 58.14; H, 2.44; N, 4.84; Found: C,
58.17; H, 2.35; N, 4.83; ESI-MS (m/z): 578.0 [M]þ.
under argon for 8 h. After cooling to room temperature, the
reaction mixture was filtered to remove the insoluble potas-
sium fluoride. The filtrate was concentrated on a rota-evapo-
rator to about 1 mL. To the residue was added methanol (4
mL) to yield a white crystalline product, which was collected
by filtration, washed thoroughly with distilled water and
2,5-Bis(2,3,5-trifluoro-4,6-bis(p-tolyloxy)phenyl)-1,3,
4-oxadiazole (4T-FPOx)
A mixture of FPOx (0.803 g, 1.997 mmol), p-cresol (1.070 g,
9.898 mmol) and anhydrous potassium fluoride (1.152 g,
19.827 mmol) in anhydrous DMF (20 mL) was prepared and
stirred at 60 ꢀC under argon for 8 h. After cooling to room
temperature, the reaction solution was poured into a mixture
of methanol and distilled water (200 mL, 1:1, v/v).
The resulting precipitates were collected by filtration,
washed thoroughly with distilled water and methanol, and
recrystallized from toluene/methanol (15/85, v/v) to give
white needle-like crystals (1.3 g, 87% yield): mp. 128–129
ꢀC; 1H NMR (400 MHz, CDCl3): d 7.13 (d, 4H, J ¼ 8.4 Hz),
7.02 (d, 4H, J ¼ 8.4 Hz), 6.89 (d, 4H, J ¼ 8.8 Hz), 6.74 (d,
4H, J ¼ 8.4 Hz), 2.33 (s, 3H), 2.27 (s, 3H); 13C NMR (100
MHz, CDCl3): d 157.1–157.2 (m), 155.3, 154.8, 146.0 (dm,
1
1JF-C ¼ 260 Hz), 142.2 (dm, JF-C ¼ 251 Hz), 138.9–139.1
(m), 137.2–137.5 (m), 133.7, 133.0, 130.2, 130.0, 115.6,
115.4, 105.2–105.4 (m) 20.6, 20.5; 19F NMR (282 M, CDCl3):
d ꢁ58.6 (dd, 2F, J ¼ 21.4 Hz, J ¼ 10.4 Hz), ꢁ64.2 (d, 2F, J ¼
10.4 Hz), ꢁ73.7 (d, 2F, J ¼ 21.4 Hz); FTIR (KBr, cmꢁ1):
FIGURE 5 The second DSC heating curves of P1 and p-toly-
loxylated polymers (P1-a–P1-d) in nitrogen with a heating rate
of 10 ꢀC/min.
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SCHEME 3 Polymerization of 2T-FPOx and one-pot synthesis of grafted polymers with different topologies.
TABLE 2 Characterizations of Polymers Synthesized via One-Pot One-Step or Two-Step
Method
Feed
Ratioa
Yield
(%)
Mn
(ꢂ104)b
Tg
(ꢀC)c
Td
(ꢀC)d
Polym.
Monomer
PDIb
P1-a0
P1-b0
P2
(FPOxþ6FBPA)þp-cresole
(FPOxþ6FBPA)þp-cresole
2T-FPOxþ6FBPA
1:1:1
1:1:2
1:1
90
88
85
90
94
93
4.9
6.2
1.5
0.6
1.5
1.6
2.6
2.4
1.7
2.4
5.9
4.8
158
143
132
129
151
124
428
431
414
405
457
437
P20
(FPOxþp-cresol)þ6FBPAe
FPOxþ6FBPAþp-cresolf
FPOxþ6FBPAþp-cresolf
1:2:1
1:1:1
1:1:2
P3-a
P3-b
a
Molar feed ratio of monomers.
b
c
d
e
f
Number-average molecular weight (Mn) and polydispersity (PDI) determined by GPC.
Glass transition temperature measured by DSC in nitrogen at a heating rate of 10 ꢀC/min.
Onset temperature for 5% weight loss measured by TGA in nitrogen at a heating rate of 20 ꢀC/min.
One-pot two-step polymerization.
One-pot one-step polymerization.
MULTIFUNCTIONALITY OF PERFLUORINATED ARYL COMPOUND, ZHAO ET AL.
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JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
FIGURE 6 Illustration of different topologies of P1-b, P2, and P3-b.
methanol, and recrystallized from toluene/menthol (15/85,
v/v) to give white needle crystals (1.2 g, 83% yield).
4H, J ¼ 8.4 Hz), 2.29 (s, 6H), 2.26 (s, 12H); 13C NMR (100
1
M, CDCl3): d 157.9 (m), 155.5, 154.9, 146.5 (dd, JF-C ¼ 252
3
2
4
Hz, JF-C ¼ 3.5 Hz), 139.8 (dd, JF-C ¼ 11.6 Hz, JF-C ¼ 4.2
2
Hz), 136.9 (t, JF-C ¼ 13.3 Hz), 133.3, 132.7, 130.1, 129.9,
2,5-Bis(3,5-difluoro-2,4,6-tris(p-tolyloxy)phenyl)-1,
3,4-oxadiazole (6T-FPOx)
115.7, 115.4, 111.3, 20.59, 20.57; 19F NMR (282 MHz,
CDCl3): d ꢁ63.6 (s, 4F); FTIR (KBr, cmꢁ1): 3033, 2919, 1879,
1601, 1470, 1205, 988, 846, 811, 486; Anal. Calcd. for
A mixture solution of FPOx (0.517 g, 1.285 mmol), p-cresol
(1.130 g, 10.453 mmol) and anhydrous potassium fluoride
(0.89 g, 15 mmol) in anhydrous DMF (12 mL) was prepared
and stirred at 160 ꢀC under argon for 8 h. After cooling
to room temperature, the reaction mixture was filtered
and the filtrate was concentrated on a rota-evaporator to
about 1 mL.
C
56H42F4N2O7: C, 72.25; H, 4.55; N, 3.01; Found: C, 71.90; H,
4.66; N, 2.95; ESI-MS (m/z): 931.1 [MþH]þ.
Synthesis of Polymers
P1: To a solution of FPOx (1.522 g, 3.784 mmol) and 6F-BPA
(1.272 g, 3.784 mmol) in anhydrous DMF (22 mL) was
added anhydrous potassium fluoride (0.922 g, 15.89 mmol).
The resulting mixture was stirred at room temperature
under argon for 90 min before additional FPOx (0.103 g,
0.25 mmol) was added to the solution to end-cap the poly-
mer chains. The solution was stirred for another 2 h and
then dropped into a methanol/distilled water mixture (300
mL, 1:1, v/v). The resulting polymer precipitates were
To the residue was added methanol (4 mL) to precipitate
the white crystalline product, which was collected by filtra-
tion, washed thoroughly with distilled water and methanol,
and recrystallized from toluene/menthol (15/85, v/v) to
give white needle crsytals (1.1 g, 93% yield): mp. 129–130
ꢀC; 1H NMR (400 MHz, CDCl3): d 7.09 (d, 4H, J ¼ 8.4 Hz),
6.96 (d, 8H, J ¼ 8.4 Hz), 6.84 (d, 4H, J ¼ 8.4 Hz), 6.67 (d,
FIGURE
7
1H NMR (400 MHz,
CDCl3) spectra of P1-b, P2 and
P3-b.
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ARTICLE
collected by filtration and thoroughly washed with distilled
water and methanol. To ensure a complete removal of any
trapped impurities, the polymer was redissolved in tetrahy-
drofuran (9 mL) and reprecipitated in the methanol/water
mixture (200 mL, 1:1, v/v), followed by Soxhlet extraction
with methanol for 10 h.
a stirring methanol/distilled water mixture (30 mL, 1:1, v/v)
to precipitate the polymer.
The following work-up procedure was the same as that for
P1: 0.260 g, 85% yield; Mn ¼ 21000, PDI ¼ 2.7 (GPC); 1H
NMR (400 MHz, CDCl3): d 7.36 (d, J ¼ 8.4 Hz), 6.95–7.04
(m), 6.75 (d, J ¼ 8.4 Hz), 6.68 (d, J ¼ 8.4 Hz), 2.26 (s); 19F
The polymer was then dried at 60 ꢀC in a vacuum oven
NMR (282 MHz, CDCl3): d 13.6 (s), ꢁ57.9 (s br), ꢁ62.5 to
1
ꢀ
(2.48 g, 90% yield): Mn ¼ 21000, PDI ¼ 2.4 (GPC); H NMR
ꢁ64.3 (m), ꢁ73.0 to ꢁ73.1 (m); Tg ¼ 128 C (DSC); Td,5%
¼
ꢀ
(400 MHz, CDCl3): d 7.40 (d, 4H, J ¼ 8.1 Hz), 7.06 (d, 4H, J
¼ 8.1 Hz); 19F NMR (282 MHz, CDCl3): d 13.6 (s, 6F), ꢁ56.5
(m, 4F, ArAF meta to Ox), ꢁ73.0 (m, 4F, ArAF ortho to Ox);
FTIR (KBr, cmꢁ1): 1653, 1607, 1510, 1482, 1219, 1173, 992,
417 C (TGA).
P1-d (Grafting of p-cresol, Feed Ratio of
p-cresol/Repeat Unit ¼ 4:1)
To a solution of P1 (0.162 g, 0.232 mmol of repeat unit) and
p-cresol (0.102 g, 0.943 mmol) in anhydrous DMF (3 mL)
was added anhydrous potassium fluoride (0.080 g, 1.377
mmol). The mixture solution was heated under agron to 160
ꢀC and stirred at the temperature for 8 h. After cooling to
room temperature, the mixture solution was dropped into
methanol/distilled water mixture (30 mL 1:1, v/v) to precip-
itate the polymer.
ꢀ
ꢀ
931, 844; Tg ¼ 175 C (DSC); Td,5% ¼ 477 C (TGA).
P1-a (Grafting of p-cresol, Feed Ratio of
p-cresol/Repeat Unit ¼ 1:1)
To a solution of P1 (0.223 g, 0.319 mmol of repeat unit), p-
cresol (0.034 g, 0.314 mmol) in anhydrous DMF (4 mL) was
added anhydrous potassium fluoride (0.074 g, 1.274 mmol).
The mixture solution was heated under agron to 60 ꢀC and
stirred at the temperature for 8 h. After cooling to room
temperature, the mixture solution was dropped into a meth-
anol/distilled water mixture (30 mL, 1:1, v/v) to precipitate
the polymer.
The following work-up procedure was the same as that for
P1: 0.211 g, 88% yield; Mn ¼ 16100, PDI ¼ 2.6 (GPC); 1H
NMR (400 MHz, CDCl3): d 7.32–7.34 (m), 6.96–7.02 (m),
6.75 (d, J ¼ 8.4 Hz), 6.67 (d, J ¼ 8.4 Hz), 2.25 (s); 19F NMR
ꢀ
(282 MHz, CDCl3): d 13.7 (s, 6F), ꢁ63.1 (s, 4F); Tg ¼ 119 C
The work-up procedure was the same as that for P1: 0.211
g, 84% yield; Mn ¼ 20,600, PDI ¼ 2.6 (GPC); 1H NMR (400
MHz, CDCl3): d 7.39 (s br), 6.98–7.08 (m), 6.82 (d, J ¼ 8.4
Hz), 6.75 (d, J ¼ 8.4 Hz), 2.26 (s); 19F NMR (282 MHz,
CDCl3): d 13.6 (s), ꢁ57.0 to ꢁ57.7 (m), ꢁ63.6 to ꢁ63.7 (m),
ꢁ72.5 to ꢁ73.7 (m); Tg ¼ 149 ꢀC (DSC); Td,5% ¼ 458 ꢀC
(TGA).
ꢀ
(DSC); Td,5% ¼ 410 C (TGA).
P2 (Polymerization of 2T-FPOx with 6F-BPA)
To a solution of 2T-FPOx (2.278 g, 3.940 mmol) and 6F-BPA
(1.324 g, 3.938 mmol) in anhydrous DMF (15 mL) was
added anhydrous potassium fluoride (1.142 g, 19.655
mmol). The mixture solution was heated under agron to 60
ꢀC and stirred at the temperature for 8 h. After cooling to
room temperature, the mixture solution was dropped into a
methanol/distilled water mixture (200 mL, 1:1, v/v). The
resulting polymer precipitates were collected by filtration
and thoroughly washed with distilled water and methanol.
To further purify the polymer, the solid product was redis-
solved in tetrahydrofuran (15 mL) and reprecipitated in the
methanol/water mixture (200 mL, 1:1, v/v), followed by a
Soxhlet extraction with methanol for 10 h.
P1-b (Grafting of p-cresol, Feed Ratio of
p-cresol/Repeat Unit ¼ 2:1)
To a solution of P1 (0.307 g, 0.439 mmol of repeat unit) and
p-cresol (0.095 g, 0.878 mmol) in anhydrous DMF (5 mL)
was added anhydrous potassium fluoride (0.102 g, 1.755
mmol). The mixture solution was heated under argon to 60
ꢀC and stirred at the temperature for 8 h. After cooling to
room temperature, the mixture solution was dropped into
methanol/distilled water mixture (30 mL 1:1, v/v) to precip-
itate the polymer.
The polymer was then dried at 60 ꢀC in a vacuum oven
1
(3.05 g, 85% yield): Mn ¼ 15100, PDI ¼ 1.7 (GPC); H NMR
The following work-up procedure was the same as that for
P1: 0.352 g, 91% yield; Mn ¼ 21,600, PDI ¼ 2.9 (GPC); 1H
NMR (400 MHz, CDCl3): d 7.36 (d, J ¼ 8.4 Hz), 7.05 (m),
6.75 (d, J ¼ 8.4 Hz), 2.26 (s); 19F NMR (282 MHz, CDCl3): d
13.6 (s), ꢁ56.0 to ꢁ57.9 (m), ꢁ63.6 to ꢁ63.7 (m), ꢁ72.9 to
(400 MHz, CDCl3): d 7.25 (s br, 4H), 7.10 (m, 4H), 6.85 (m,
8H), 2.28 (s, 6H); 19F NMR (282 MHz, CDCl3): d 13.5 (s),
ꢁ58.2 (m), ꢁ63.7 (m), ꢁ72.3 (m); FTIR (KBr, cmꢁ1): 3043,
2929, 1608, 1550, 1179, 1088, 991, 842, 733, 595; Tg ¼ 132
ꢀ
ꢀC (DSC); Td,5% ¼ 414 C (TGA).
ꢀ
ꢀ
ꢁ73.7 (m); Tg ¼ 135 C (DSC); Td,5% ¼ 436 C (TGA).
P3-a (One-Step Synthesis of Random-Topology Polymer,
FPOx/6F-BPA/p-cresol Feed Ratio ¼ 1:1:1)
P1-c (Grafting of p-cresol, Feed Ratio of
p-cresol/Repeat Unit ¼ 3:1)
To a solution of FPOx (0.969 g, 2.409 mmol), 6F-BPA (0.810
g, 2.409 mmol) and p-cresol (0.262 g, 2.423 mmol) in anhy-
drous DMF (12 mL) was added anhydrous potassium fluo-
ride (0.699 g, 12.031 mmol). The mixture solution was
To a solution of P1 (0.250 g, 0.358 mmol of repeat unit) and
p-cresol (0.116 g, 1.073 mmol) in anhydrous DMF (4 mL)
was added anhydrous potassium fluoride (0.104 g, 1.790
mmol). The mixture solution was heated under argon to
ꢀ
heated under agron to 60 C and stirred at the temperature
ꢀ
110 C and stirred at the temperature for 8 h. After cooling
for 8 h. After cooling to room temperature, the mixture solu-
tion was dropped into methanol/distilled water mixture
to room temperature, the mixture solution was dropped into
MULTIFUNCTIONALITY OF PERFLUORINATED ARYL COMPOUND, ZHAO ET AL.
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JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
(200 mL, 1:1, v/v) to precipitate the polymer, which was
then collected by filtration, thoroughly washed with distilled
water and methanol. To ensure the complete removal of any
trapped impurities, the polymer was redissolved into tetra-
hydrofuran (10 mL) and reprecipitated into methanol/dis-
tilled water mixture (200 mL, 1:1, v/v), followed by Soxhlet
extraction with methanol for 10 h.
added anhydrous potassium fluoride (0.561 g, 9.656 mmol).
The mixture solution was stirred at room temperature under
agron for 80 min before p-cresol (0.523 g, 4.838 mmol) was
added. The reaction mixture was then heated to 60 ꢀC and
stirred at the temperature for 8 h. After cooling to room
temperature, the mixture solution was dropped into metha-
nol/distilled water mixture (200 mL 1:1, v/v) to precipitate
the polymer.
The polymer was then dried at 60 ꢀC in a vacuum oven
1
(1.32 g, 94% yield): Mn ¼ 14500, PDI ¼ 5.9 (GPC); H NMR
The following work-up procedure was the same as that for
P1: 1.85 g, 88% yield; Mn ¼ 61700, PDI ¼ 2.4 (GPC); 1H
NMR (400 MHz, CDCl3): d 7.37 (s, 4H), 7.07–7.00 (m, 8H),
6.81, 6.74 (m, 4H), 2.33, 2.26 (6H); 19F NMR (282 MHz,
CDCl3): d 13.7 (s), ꢁ57.4 (m), ꢁ63.4 (m), ꢁ73.4 (m); FTIR
(KBr, cmꢁ1): 3049, 2928, 1649, 1607, 1480(br), 1219, 1175,
(400 MHz, CDCl3): d 7.38 (s br, 4H), 6.75–7.14 (m, 8H), 2.34
(s, ?H), 2.26 (s, ?H); 19F NMR (282 MHz, CDCl3): d 13.8 (s),
ꢁ57.8 (m), ꢁ63.4 (m), ꢁ73.5 (m); FTIR (KBr, cmꢁ1): 2927,
1648, 1608, 1483(br), 1220, 1176, 1086, 994, 936, 845,
ꢀ
ꢀ
736; Tg ¼ 151 C (DSC); Td,5% ¼ 457 C (TGA).
ꢀ
1085, 992, 936, 845, 737, 631, 519; Tg ¼143 C (DSC); Td,5%
P3-b (One-Step Synthesis of Random-Topology Polymer,
FPOx/6F-BPA/p-cresol Feed Ratio ¼ 1:1:2)
ꢀ
¼ 431 C (TGA).
To a solution of FPOx (0.933 g, 2.320 mmol), 6F-BPA (0.780
g, 32.320 mmol) and p-cresol (0.502 g, 4.643 mmol) in anhy-
drous DMF (16 mL) was added anhydrous potassium fluo-
ride (0.808 g, 13.907 mmol). The mixture solution was
P20 (One-Pot Two-Step Synthesis of Polymer
P2 from FPOx)
To a solution of FPOx (0.925 g, 2.300 mmol) and p-cresol
(0.498 g, 4.606 mmol) in anhydrous DMF (8 mL) was added
anhydrous potassium fluoride (0.536 g, 9.2 mmol). The mix-
ture solution was stirred at room temperature under agron
for 120 min before 6F-BPA (0.773 g, 2.299 mmol) and anhy-
drous potassium fluoride (0.268 g, 4.6 mmol) were added.
The reaction mixture was then heated to 60 ꢀC and stirred
at the temperature for 8 h. After cooling to room tempera-
ture, the mixture solution was dropped into methanol/dis-
tilled water mixture (200 mL 1:1, v/v) to precipitate the
polymer.
ꢀ
heated under agron to 60 C and stirred at the temperature
for 8 h. After cooling to room temperature, the mixture solu-
tion was dropped into methanol/distilled water mixture
(200 mL 1:1, v/v) to precipitate the polymer.
The following work-up procedure was the same as that for
P3-a: 2.03 g, 93% yield; Mn ¼16500, PDI ¼ 4.8 (GPC); 1H
NMR (400 MHz, CDCl3): d 7.35 (s br, 4H), 6.74–7.13 (m, 12H),
2.32 (s, ?H), 2.25 (s, ?H); 19F NMR (282 MHz, CDCl3): d 13.5
(s), ꢁ58.1 (m), ꢁ63.8 (m), ꢁ74.1 (m); FTIR (KBr, cmꢁ1):
3044, 2929, 1642, 1607, 1501(br), 1215, 1176, 1083, 992,
ꢀ
ꢀ
The following work-up procedure was the same as that for
936, 846, 736; Tg ¼124 C (DSC); Td,5% ¼ 437 C (TGA).
1
P1: 1.69 g, 90% yield; Mn ¼ 5500, PDI ¼ 2.4 (GPC); H NMR
P1-a0 (One-Pot Two-Step Synthesis of Grafted Polymer P1-
a, FPOx/6F-BPA/p-cresol Feed Ratio ¼ 1:1:1)
(400 MHz, CDCl3): d 7.28 (s br, 4H), 7.12 (m, 4H), 6.84–6.90
(m, 8H), 2.29 (s, 6H); 19F NMR (282 MHz, CDCl3): d 13.6 (s),
ꢁ58.4 (m), ꢁ63.7 (m), ꢁ72.3 (m); FTIR (KBr, cmꢁ1): 3042,
2928, 1641, 1607, 1503, 1412, 1174 (br), 1085, 990, 936,
846, 734, 630, 518; Tg ¼129 ꢀC (DSC); Td,5% ¼ 405 ꢀC
(TGA).
To a solution of FPOx (0.569 g, 1.415 mmol) and 6F-BPA
(0.476 g, 1.415 mmol) in anhydrous DMF (10 mL) was
added anhydrous potassium fluoride (0.410 g, 7.056 mmol).
The mixture solution was stirred at room temperature under
nitrogen for 80 min before p-cresol (0.153 g, 1.415 mmol)
was added. The reaction mixture was then heated to 60 ꢀC
and stirred at the temperature for 8 h. After cooling to room
temperature, the mixture solution was dropped into metha-
nol/distilled water mixture (200 mL 1:1, v/v) to precipitate
the polymer.
CONCLUSIONS
In summary, we have successfully demonstrated the unique
stepped multifunctionality of a perfluorinated compound,
that is, FPOx. Four levels of reactivity have been identified
for the para and ortho CAF of FPOx, which can be easily
triggered by the reaction temperature to enable quantitative
reactions with nucleophiles. The CAF at lower levels of reac-
tivity did not interfere with reactions of the CAF at higher
levels of reactivity, which makes it possible to realize clean
and hierarchically controllable reactions. The successful
applications of such a multistepped reactivity of FPOx in ver-
satile synthesis of grafted polymers with well-controlled
structures and topologies have been demonstrated.
The following work-up procedure was the same as that for
P1: 0.99 g, 90% yield; Mn ¼ 49200, PDI ¼ 2.6 (GPC); 1H
NMR (400 MHz, CDCl3): d 7.37 (s, 4H), 7.01–7.03 (m, 6H),
6.81, 6.74 (m, 2H), 2.33, 2.26 (3H); 19F NMR (282 MHz,
CDCl3): d 13.7 (s), ꢁ57.4 (m), ꢁ63.5 (m), ꢁ73.4 (m); FTIR
(KBr, cmꢁ1): 2927, 1652, 1608, 1488(br), 1225, 1178, 1086,
993, 934, 844, 738, 632, 526; Tg ¼ 158 ꢀC (DSC); Td,5%
¼
ꢀ
428 C (TGA).
P1-b0 (One-Pot Two-Step Synthesis of Grafted Polymer
P1-b, FPOx/6F-BPA/p-cresol Feed Ratio ¼ 1:1:2)
The authors thank the National Natural Science Foundation of
China (Grant Nos. 20504003 and 20774002) for the financial
support.
To a solution of FPOx (0.972 g, 2.417 mmol) and 6F-BPA
(0.813 g, 2.418 mmol) in anhydrous DMF (12 mL) was
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ARTICLE
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