ABSTRACT: A unique class of aromatic ether polymers
containing perfluorocyclopentenyl (PFCP) enchainment was
prepared from the simple step growth polycondensation of
commercial bisphenols and octafluorocyclopentene (OFCP)
in the presence of triethylamine. Model studies indicate that
the second addition/elimination on OFCP is fast and poly-
condensation results in linear homopolymers and copolymers
without side products. The synthesis of bis(heptafluoro-
cyclopentenyl) aryl ether monomers and their condensation
with bisphenols further led to PFCP copolymers with alternating structures. This new class of semifluorinated polymers exhibit surprisingly high crystallinity in some cases and excellent thermal stability.
2. polymers containing fluorinated vinyl groups are found to be
potentially reactive and thermally cross-linkable.
Octafluorocyclopentene (OFCP) is a readily available
perfluorocyclic olefin with unique chemistry. Many studies
have been reported on the reaction of OFCP with nucleophiles,
such as phenoxides,12−15
arenethiolates,16
amines,17−19
eno-
lates, phosphonium ylides,20
and organolithium reagents.20−22
Many other examples include OFCP derivatives for photo-
chromic applications.23−25
There are very few examples of
polymers of perfluorocyclopentene by traditional chain growth
mechanisms. This perfluorocyclic olefin does not homopoly-
merize under radical conditions,26
and radical copolymeriza-
tions with styrene and vinyl acetate lead to copolymers with a
very low molar ratio of perfluorocyclopentene.27
Nevertheless,
copolymerization with electron-rich monomers like vinyl ethers
leads to alternating copolymers.26,27
Step growth polymer-
ization of OFCP with bis(silyl) ethers was reported, but the
resulting polymers exhibited low molecular weight.28
To our
knowledge, the polycondensation of bisphenols with perfluoro-
cycloolefins has not been previously reported.
■ RESULTS AND DISCUSSION
Prior to polycondensation, a model reaction was performed
using OFCP and sodium phenoxide (Scheme 3). Interestingly,
75% of the clean product mixture was the bis adduct as
determined by 19
F NMR spectroscopy, most likely due to
increased solubility of the monoadduct (Figure 1).
Polycondensation was attempted using the sodium salt of
bis(hydroxyphenyl)hexafluoroisopropylidene (Bisphenol AF)
and OFCP in DMF at 80 °C for 10 h. Low-molecular-weight
oligomers were obtained. Thus, an alternative method was
explored using triethylamine as the base (Scheme 1) to afford
perfluorocyclopentenyl (PFCP) aryl ether homopolymer P1 of
number-average molecular weight and PDI of 9100 g mol−1
and
2.5, respectively (Table 1).
Moreover, homopolymer P1 was determined to be
hydroxytelechelic by the absence of 19
F NMR signals centered
at −149 ppm representative of the fluoroolefin (Figure 2b).
In the 1
H NMR spectrum (Figure 2a), there are two signals
representing aromatic (6.9 and 7.3 ppm) protons, as expected.
These signals (dd, J = 8.8 Hz) indicate a symmetric environ-
ment around both ether linkages of the PFCP rings and
support an addition−elimination reaction which leaves the
double bond of the PFCP ring intact. Further, 19
F NMR shows
three clean signals, corresponding to three unique fluorine
atoms in symmetrical environments, as expected (Figure 2b). A
PFCP end-capped polymer was also prepared by the addition
of an excess of OFCP at the end of the reaction.
PFCP aryl ether homopolymer P2 was prepared from
Bisphenol A via the same methodology as P1 (Scheme 1). For
homopolymer P2, the number-average molecular weight and
PDI were 9600 and 1.15 after 24 h reaction time (Table 1).
Homopolymer P2 was characterized by 1
H NMR and
19
F NMR spectroscopy and, as before, exhibited a clean
addition−elimination polycondensation (Figure 3). 1
H NMR
shows symmetric aromatic groups and a clean singlet for the
methyl protons (1.57 ppm). 19
F NMR shows only two
resonances corresponding to the PFCP ring substituted in a
symmetrical fashion.
PFCP aryl ether homopolymer P3 was prepared from
biphenol under similar conditions (Scheme 1). P3 shows a
Scheme 3. Model Reaction between OFCP and Sodium
Phenoxide
Figure 1. 19
F NMR spectrum of the model reaction product mixture.
Table 1. PFCP Polymers Molecular Weight, Polydispersity
Index (PDI), Thermal Properties, and Yield of
Polymerization
PFCP Mn Mw PDIa
Tg (°C)b
Td5%
(°C)c
yield
(wt %)
homopolymer P1 9100 22900 2.5 124 483 70
homopolymer P2 9600 11100 1.1 89 432 54
homopolymer P3 15450 29800 1.9 105 460 90
P3-co-P1d
5900 9300 1.5 94 325 74
copolymer (M1-alt-BP) 8400 14500 1.7 98 310 69
copolymer (M2-alt-6F) 2000 3000 1.5 68 224 51
a
GPC in THF using polystyrene as standard after precipitation in
methanol. b
DSC (heating rate 10 °C/min) in a nitrogen atmosphere.
c
TGA (heating rate 10 °C/min) in a nitrogen atmosphere. d
0.49/0.51
molar ratio of monomer 1/2 in copolymer as determined by 19
F NMR
spectroscopy.
Figure 2. (a) 1
H NMR and (b) 19
F NMR of PFCP aryl ether
homopolymer P1.
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3. higher number-average molecular weight of 15 450, with a PDI
of 1.9 (Table 1), relative to the above-mentioned homopoly-
mers (P1 and P2), with clean and well-integrated signals in
1
H NMR and 19
F NMR spectroscopy (Figure 4).
1
H and 19
F NMR spectra show no evidence of chiral carbon
atoms within the cyclopentene ring as would be expected in the
case of an addition rather than an addition−elimination
reaction. PFCP homopolymers (P1, P2, and P3) show
absorption in the ultraviolet spectrum (λmax 210 nm for P1,
P2 and 260 nm for P3) with no corresponding fluorescence.
Thermal analysis of these polymers shows unexpected
properties (Table 1). P1 exhibits a glass transition temperature
(Tg) of 124 °C, as determined by DSC, and a polymorphic
crystallization and melting at ca. 218 and 250 °C, respectively
(Figure 5a). The decomposition temperature (Td) at 5% weight
loss determined by thermogravimetric analysis (TGA) under
N2 was 483 °C for P1 with a number-average molecular weight
of 9100 (Figure 6). Remarkably, homopolymer P1 exhibited an
exceptional char yield of greater than 85% up to 800 °C.
DSC thermograms for P2 exhibited a glass transition temper-
ature of 89 °C. However, unlike P1, PFCP polymer P2 does not
show crystallinity under these conditions (Figure 5b), presumably
due to the decreased fluorine content as analogously observed for
the 6F-PFCB polymer.29
TGA analysis under a N2 atmosphere
shows that the decomposition temperature (Td) at 5% weight
loss exceeds 430 °C (Figure 6).
Figure 3. (a) 1
H NMR and (b) 19
F NMR of PFCP aryl ether
homopolymer P2.
Figure 4. 1
H NMR and 19
F NMR of PFCP aryl ether homopoly-
mer P3.
Figure 5. DSC thermograms of PFCP aryl ether homopolymer (a) P1,
(b) P2, and (c) P3.
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4. PFCP aryl ether homopolymer P3 exhibited an endothermic
transition determined by DSC of 105 °C (Figure 5c). Like P2
and unlike P1, P3 does not show crystallinity or melting
behavior under these conditions (Figure 5c). This higher
molecular weight homopolymer P3 gave decomposition
temperature of 460 °C (Td at 5% weight loss, Figure 6).
A random PFCP copolymer was also prepared in one step
with bisphenols and OFCP (Table 1). Reactions of variable
bisphenols with a slight excess of OFCP led to novel bis-
(heptafluorocyclopentenyl) aryl ether monomers (M1, M2)
and their step growth polymerization with other bisphenols
afforded PFCP copolymers with alternating arylene ether
structures (Scheme 4).
As seen earlier, biphenol gave higher molecular weight than
Bisphenol AF during polymerization with OFCP (P3 vs P1).
This may be due to the electron-withdrawing effect of the CF3
groups decreasing its nucleophilicity compared to biphenol.
Likewise, alternating copolymers of 6F containing monomer
M1 gave the highest molecular weight for identical copolymer
structures of different monomers (Table 1). This method
demonstrates a modular approach to alternating copolymers
from monomers of variable reactivity. Further, because of its
higher molecular weight, copolymer M1-alt-BP exhibits more
robust thermal properties than copolymer M2-alt-6F.
■ CONCLUSION
We have developed a step growth polymerization of bisphenols
with OFCP toward synthesis of a new class of perfluorocyclo-
pentenyl (PFCP) aryl ether polymers from commercial
feedstocks. PFCP polymers can be easily modified and func-
tionalized by using bisphenols with different spacer functional
groups. PFCP polymers exhibited very interesting thermal
properties with variable Tg depending upon the chosen
bisphenol. These polymers were obtained in good yields and
show high thermal stabilities under N2 with Td at 5% weight
loss ranging from 432 to 483 °C for homopolymers and 224 to
325 °C for copolymers. This new family of semifluorinated aryl
ether polymers can easily have phenolic or perfluorocyclopen-
tenyl terminal groups depending on the stoicheometry of the
reactants. Further, PFCP polymers contain main chain vinyl
ether groups for postpolymerization modification and potential
cross-linking.
■ EXPERIMENTAL SECTION
Chemical Reagents. Octafluorocyclopentene (99%) was pur-
chased from Synquest Laboratories and used as received. Bis-
(hydroxyphenyl)hexafluoroisopropylidene (Bisphenol AF) and 4,4′-
biphenol were donated by Tetramer Technologies, L.L.C., Pendelton,
SC. Deuterated solvents were purchased from Mallinckrodt Chemicals
Inc. All other chemicals and solvents (analytical grade) were purchased
from Sigma-Aldrich and used as received unless otherwise stated.
Instrumentation. M1 and M2 and copolymers were characterized
on a JEOL ECX-300 MHz NMR spectrometer via 1
H, 19
F, and
proton-fluorine decoupled 13
C spectroscopy. P1, P2, and P3 were
characterized on a Bruker 400 MHz NMR spectrometer via 1
H, proton
decoupled 19
F, and proton decoupled 13
C spectroscopy. Chemical
shifts were measured in ppm (δ) with reference to internal
tetramethylsilane (0 ppm), deuterated chloroform (77 ppm)/
deuterated tetrahydrofuran (25.3 ppm)/deuterated acetone (29.8
ppm), and trichlorofluoromethane (0 ppm) for 1
H, 13
C, and 19
F NMR,
respectively. For coupled spectra, values are reported from the center
of the pattern. Attenuated total reflectance Fourier transform infrared
(ATR-FTIR) analyses of neat samples were performed on a Thermo-
Nicolet Magna 550 FTIR spectrophotometer with a high endurance
diamond ATR attachment. Ultraviolet−visible absorption and fluore-
scence spectroscopy were measured in THF on an Agilent 8453 UV−
vis spectroscopy system and Perkin-Elmer LS 50 B luminescence
spectrometer, respectively. Differential scanning calorimetry (DSC)
analysis was performed on a Mettler Toledo DSC 1 system in nitrogen
at a heating rate of 10 °C/min. The glass transition temperature (Tg)
was obtained from a second heating cycle using Star E version 10.0
software suite. Thermal gravimetric analysis (TGA) was performed on
a Mettler-Toledo TGA/DSC 1 LF instrument in nitrogen at a heating
rate of 10 °C/min up to 800 °C. Molecular weights for polymers P1,
P2 and P3 were measured by size exclusion chromatography (SEC)
analysis on a Viscotek VE 3580 system equipped with a ViscoGEL
column (GMHHR-M), connected to a refractive index (RI) detector.
GPC solvent/sample module (GPCmax) was used with HPLC grade
THF as the eluent and calibration was based on polystyrene standards.
For copolymers, gel permeation chromatography (GPC) data were
collected in THF from a Waters 2690 Alliance System with photo-
diode array detection. GPC samples were eluted in series through
Polymer Laboratories PLGel 5 mm Mixed-D and Mixed-E columns at
35 °C. Molecular weights were obtained using polystyrene as a
standard (Polymer Laboratories Easical PS-2).
Synthesis of PFCP Aryl Ether Homopolymer P1. In a 25 mL
Schlenk tube equipped with a magnetic stirrer was added 1.00 g
(2.97 mmol) of Bisphenol AF, 0.662 g (6.54 mmol) of triethylamine,
and 10 mL of DMF. The solution was degassed with nitrogen for
10 min, and 0.631 g (2.97 mmol) of octafluorocyclopentene was added
via syringe; the Schlenk flask was heated slowly to 80 °C for 24 h. The
polymer was then precipitated in 100 mL of methanol, filtered, washed
several times with methanol, and dried under vacuum at 50 °C for
24 h, giving 1.1 g of a white powder (yield = 74%). 1
H NMR
(400 MHz, THF-d8, δ): 6.91 (dm, 3
JH‑2(H‑1) = 8.80 Hz, 4H), 7.32 (dm,
3
JH‑1(H‑2) = 8.80 Hz, 4H). 19
F NMR (376 MHz, THF-d8, δ): −63.85
(6F), −115.13 (4F), −130.17 (2F). 13
C NMR (100 MHz, THF-d8, δ):
Figure 6. TGA thermograms of PFCP aryl ether homopolymers P1,
P2, and P3.
Scheme 4. Bis(heptafluorocyclopentenyl) Aryl Ether
Monomers Synthesis and Polymerization
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5. 64.6, 110.8 (PFCP, CF2), 113.8 (PFCP, CF2), 117.5, 125.2, 130.8,
132.7, 134.9 (PFCP, CC), 155.2. FTIR (ν, cm−1
): 3150 and 3063
(H−CC), 1274 (C−O), 1151 (C−F), 780 and 658 (C−F).
Synthesis of PFCP Aryl Ether Homopolymer P2. Homopol-
ymer P2 was synthesized using the same method as P1, except it was
precipitated in a 0.5/0.5 volume ratio of water/methanol and washed
several times with a solution of 0.5/0.5 volume ratio of water/
methanol, giving a white powder after drying (yield = 90%). 1
H NMR
(400 MHz, acetone-d6, δ): 1.51 (dm, 6H), 6.69 (dm, 3
JH‑2(H‑1) = 8.91
Hz, 4H), 7.08 (dm, 3
JH‑1(H‑2) = 8.91 Hz, 4H). 19
F NMR (376 MHz,
acetone-d6, δ): −114.20 (4F), −129.71 (2F). 13
C NMR (100 MHz,
THF-d8, δ): 31.0, 42.7, 110.6 (PFCP, CF2), 114.1 (PFCP, CF2), 117.1,
128.5, 134.8 (PFCP, CC), 147.8, 153.0. FTIR (ν, cm−1
): 3130 and
3065 (H−CC), 1272 (C−O), 1142 (C−F), 782 and 654 (C−F).
Synthesis of PFCP Aryl Ether Homopolymer P3. Homopol-
ymer P3 was synthesized using the same method as P2, except the
reaction time was 36 h, giving a white powder after drying (yield =
50%). 1
H NMR (400 MHz, acetone-d6, δ): 6.92 (dm, 3
JH‑2(H‑1) = 8.58
Hz, 4H), 7.31(dm, 3
JH‑1(H‑2) = 8.58 Hz, 4H). 19
F NMR (376 MHz,
acetone-d6, δ): −113.89 (4F), −129.60 (2F). 13
C NMR (100 MHz,
acetone-d6, δ): 110.5 (PFCP, CF2), 114.0 (PFCP, CF2), 118.5, 128.8,
135.0 (PFCP, CC), 137.7, 154.5. FTIR (ν, cm−1
): 3151 and 3070
(H−CC), 2941 (C−H), 1270 (C−O), 1150 (C−F), 780 and 653
(C−F).
Synthesis of P3-co-P1. In a 25 mL Schlenk tube equipped with a
magnetic stirrer was added 0.793 g (2.36 mmol) of Bisphenol AF,
0.439 g (2.36 mmol) of biphenol, 1.052 g (10.39 mmol) of
triethylamine, and 10 mL of DMF. The solution was degassed with
argon for 10 min, and 0.631 g (2.97 mmol) of octafluorocyclopentene
was added via syringe; the Schlenk flask was heated at 80 °C for 10 h.
The dissolved polymer was then precipitated in 100 mL of 0.5/0.5
volume ratio of water/methanol and washed several times with a
solution of 0.5/0.5 volume ratio of water/methanol and dried under
vacuum at 50 °C for 24 h, giving 1.7 g of a white powder (yield =
74%). 1
H NMR (300 MHz, acetone-d6, δ): 7.15 (m). 19
F NMR (282
MHz, acetone-d6, δ): −64.44 (m, 3F), −115.21 (m, 4F), −130.61 (m,
2F). FTIR (ν, cm−1
): 3150 and 3075 (H−CC), 1273 (C−O), 1150
(C−F), 787 and 661 (C−F).
Synthesis of M1. To a 50 mL round-bottom flask equipped with
a magnetic stirrer were introduced 2.00 g (5.95 mmol) of Bisphenol
AF, 2.77 g (13.1 mmol) of triethylamine, and 20 mL of DMF, and the
solution was degassed with argon for 10 min. 2.775 g (13.09 mmol) of
octafluorocyclopentene was then introduced with a syringe, and the
solution was heated slowly to 80 °C for 10 h. The solvent was then
removed, and the crude product was isolated by column
chromatography in dichloromethane (Rf = 0.93) to give 3.1 g of a
colorless oil (yield = 65%). 1
H NMR (300 MHz, CDCl3, δ): 7.19
(d, 3
JH‑1(H‑2) = 8.58 Hz, 4H), 7.43 (d, 3
JH‑1(H‑2) = 8.58 Hz, 4H).
19
F NMR (282 MHz, CDCl3, δ): −63.91 (s, 6F), −115.32 (d, 3
JF1(F‑2) =
9.84 Hz, 4F), −115.65 (d, 3
JF‑1(F‑2) = 13.11 Hz, 4F), −129.39 (s, 4F),
−146.61 (s, 2F). 13
C NMR (75 MHz, CDCl3, δ): 67.4, 105.5, 109.1,
111.1, 112.0, 118.3, 123.9, 131.3, 131.7, 138.0, 154.1. FTIR (ν, cm−1
):
3150 and 3075 (H−CC), 1270 (C−O), 1160 (C−F), 783 and 665
(C−F). GC-MS (m/z) [M + H]+
: 720.4 Elemental analysis: Calcd
(Found) C = 41.69 (41.62), H = 1.12 (1.03), F = 52.75 (53.03).
Synthesis of M2. M2 was synthesized and isolated with the same
method as described for M1 (Rf = 0.86 in dichloromethane) to give a
white solid (yield = 69%). 1
H NMR (300 MHz, CDCl3, δ): 7.25 (dm,
3
JH‑1(H‑2) = 8.61 Hz, 4H), 7.59 (d, 3
JH‑1(H‑2) = 8.61 Hz, 4H). 19
F NMR
(282 MHz, CDCl3, δ): −115.32 (m, 4F), −115.36 (m, 4F), −129.36
(s, 4F), −148.85 (s, 2F). 13
C NMR (75 MHz, CDCl3, δ): 104.3, 111.4,
114.1, 118.1, 122.2, 130.2, 131.2, 131.9, 153.9. FTIR (ν, cm−1
): 3133
and 3074 (H−CC), 1272 (C−O), 1145 (C−F), 787 (C−F). GC-
MS (m/z) [M + H]+
: 570.3 Elemental analysis: Calcd (Found) C =
46.33 (46.36), H = 1.41 (1.36), F = 46.64 (46.70).
Synthesis of Copolymer (M1-alt-BP). To a 25 mL Schlenk tube
equipped with a magnetic stirrer was added 0.500 g (0.694 mmol) of
M1, 0.129 g (0.694 mmol) of biphenol, 0.155 g (1.53 mmol) of
triethylamine, and 5 mL of DMF. The solution was degassed with
argon for 10 min, and the Schlenk tube was heated slowly to 80 °C for
10 h under stirring. The dissolved polymer was then precipitated in
100 mL of 0.5/0.5 volume ratio of water/methanol and washed several
times with a solution of 0.5/0.5 volume ratio of water/methanol,
giving a white powder after drying (yield = 51%). 1
H NMR (300 MHz,
acetone-d6, δ): 6.88 (m, 8H), 7.15 (m, 4H), 7.35 (m, 4H). 19
F NMR
(282 MHz, acetone-d6, δ): −64.45 (m, 3F), −115.02 (m, 4F), −130.6
(m, 2F). FTIR (ν, cm−1
): 315 and 3090 (H−CC), 2941 (C−H),
1265 (C−O), 1150 (C−F), 790 and 658 (C−F).
Synthesis of Copolymer (M2-alt-6F). The copolymer was
prepared using the same method as copolymer M1-alt-BP, giving a
white powder after drying (yield = 69%). 1
H NMR (300 MHz,
acetone-d6, δ): 6.72 to 7.19 (m, 8H), 7.26 to 7.45 (m, 8H). 19
F NMR
(282 MHz, acetone-d6, δ): −64.18 (m, 3F), −115.37 (m, 4F), −130.54
(m, 2F). FTIR (ν, cm−1
): 3130 and 3103 (H−CC), 2960 (C−H),
1263 (C−O), 1145 (C−F), 785 (C−F).
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: dwsmith@utdallas.edu.
■ ACKNOWLEDGMENTS
The authors thank Defense Advanced Research Projects
Agency (DARPA) for funding and Tetramer Technology
LLC for the gift of bisphenols. We also thank the Robert A.
Welch Foundation (Grant AT-0041), Intel Corporation, and
The University of Texas at Dallas for partial support.
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