Synthesis of novel poly(hydroxyether terephthalate) via polyaddition of 2,5-difluoroterephthalic acid with aromatic bis(epoxide)s

Article abstract of DOI:10.1016/j.jfluchem.2008.06.028

A novel and more reliable synthetic route to 2,5-difluoroterephthalic acid was developed. A series of new poly(hydroxyether terephthalate) were prepared by the polyaddition of 2,5-difluoroterephthalic acid with various aromatic bis(epoxide)s catalyzed by tetrabutyl ammonium bromide.

Full text of DOI:10.1016/j.jfluchem.2008.06.028

Journal of Fluorine Chemistry 129 (2008) 1076–1082
Contents lists available at ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Synthesis of novel poly(hydroxyether terephthalate) via polyaddition
of 2,5-difluoroterephthalic acid with aromatic bis(epoxide)s
Xiao-Song Huang a, Feng-Ling Qing a,b,
*
a College of Chemistry, Chemical Engineering and Biotechnology, and State Key Laboratory for Modification of Chemical Fibers and Polymer Materials,
Donghua University, 2999 North Renmin Lu, Shanghai 201620, China
b Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Science, 354 Fenglin Lu, Shanghai 200032, China
A R T I C L E I N F O
A B S T R A C T
Article history:
A novel and more reliable synthetic route to 2,5-difluoroterephthalic acid was developed. A series of new
poly(hydroxyether terephthalate) were prepared by the polyaddition of 2,5-difluoroterephthalic acid
with various aromatic bis(epoxide)s catalyzed by tetrabutyl ammonium bromide.
ß 2008 Elsevier B.V. All rights reserved.
Received 30 May 2008
Received in revised form 23 June 2008
Accepted 23 June 2008
Available online 9 July 2008
Keywords:
Poly(hydroxyether terephthalate)
Aromatic bis(epoxide)s
Polyaddition
1. Introduction
additional hydrogen bond interaction between polymer chains
and how the various aromatic groups have effect on the Tg of the
Poly(hydroxyether esters) (PHEEs) are
a
class of novel
polymers. The synthesized PHETs were characterized and their
properties including thermal and solubility were also discussed
herein.
thermoplastics derived from the reaction between bis(epoxide)s
and diacids [1,2]. These polymers are of industry interest since they
can combine excellent mechanical properties with processability
and barrier properties [3]. Besides, this class of materials displays
the typical biodegradability [4,5], which makes the materials a
class of interesting candidates for environmentally benign
materials. Due to the potential applications, the investigations
on these polymers have begun to appear [6–11].
2. Results and discussion
2.1. Synthesis of 2,5-difluoroterephthalic acid (DFTA) 4
The synthesis of 2,5-difluoroterephthalic acid (DFTA) has been
reported in the early literatures. Lee et al. [18] described the
preparation of DFTA through cyanation of 1,4-dibromo-2,5-
difluorobenzene followed by acidic hydrolysis. Unfortunately,
we repeated his work only to get the product in very poor yield.
Cassidy and Reddy [19] documented the synthesis of DFTA starting
from 2,5-difluorotoluene. However, the overall yield of this
method is also not satisfactory. Thus, new synthetic route to
DFTA has to be developed in an attempt to improve the overall
yield.
Our synthetic sequence of 2,5-difluoroterephthalic acid was
outlined in Scheme 1. 2,5-Dimethyl-1,4-benzenediamine was
firstly converted to 2,5-dimethyl-1, 4-benzenebis(diazonium)
tetrafluoroborate 1 in 90% yield via Balz-Schiemann reaction.
The second step involved the dry pyrolysis of diazo salt 1 to give
2,5-difluo-p-xylene 2. Attempts to prepare compound 4 by direct
oxidation of 2 with potassium permanganate failed. Finally,
From the structural view of point, the properties of PHEE are
quite dependent on the type of both bis(epoxide)s and diacids
used. In the previous studies, the PHEEs were prepared via
diglycidyl ether of bisphenol
A with aliphatic diacids or
terephthalic acid [12–16]. It is known that hydrogen bond
can have a significant effect on the thermal properties, crystal-
lization behavior, mechanical properties, and so on of polymers
[17]. In this paper, we describe the synthesis of novel fluorine-
containing poly(hydroxyether teraphthalate) using 2,5-difluor-
oterephthaic acid (DFTA) and various aromatic bis(epoxide)s. It
is our interest to see whether the fluorine atoms can provide the
* Corresponding author at: Key Laboratory of Organofluorine Chemistry,
Shanghai Institute of Organic Chemistry, Chinese Academy of Science, 354 Fenglin
Lu, Shanghai 200032, China. Tel.: +86 21 54925187; fax: +86 21 64166128.
E-mail address: flq@mail.sioc.ac.cn (F.-L. Qing).
0022-1139/$ – see front matter ß 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2008.06.028

X.-S. Huang, F.-L. Qing / Journal of Fluorine Chemistry 129 (2008) 1076–1082
1077
Scheme 1. Synthesis of 2,5-difluoroterephthalic acid 4.
benzylic bromination of 2 with NBS followed by oxidation with 1.0
2.3. Polymer synthesis
equiv. of sodium periodate in the presence of 2% H2SO4 gave DFTA
4. To our delight, the overall yield of 2,5-difluoroterephthalic acid
as high as 50% was obtained.
The polyaddition of DFTA with aromatic bis(epoxide)s 5–10
in the presence of tetrabutylammonium bromide (TBAB)was
carried out in dioxane at 80 8C for 40 h (Scheme 3). The
corresponding polymers 11a–f were obtained in 65–83% yields.
In all of these cases, the reaction mixture was consistently
homogeneous, with products remaining in the solution. The
chemical structures of polymers 11a–f were characterized by
FT-IR, 1H NMR and 19F NMR spectroscopy. Shown in Fig. 1 is the
FT-IR spectrum of 11a. The absorption band at 3500–3400 cmꢀ1
was ascribed to the stretching vibrations of hydroxyl group
which reflect the wide distribution of hydrogen-bonded hydro-
xyl stretching frequencies. The peak at 1731 cmꢀ1 was
attributable to the symmetrical carbonyl stretching vibrations.
The C-F multiple stretching absorptions were also detected in
the range of 1300–1100 cmꢀ1. From the 1H NMR spectrum
2.2. Synthesis of aromatic bis(epoxide)s 5–10
The aromatic bis(epoxide)s 5–10 (Table 1) were prepared
by a standard procedure [20,21] in which the appropriate
bisphenol was treated with an excess of epichlorohydrin in the
presence of benzyltriethylammonium chloride (Scheme 2).
Initially, the phenolic functionalities react with the epichlor-
ohydrin to yield chlorohydrin and epoxide intermediate species
over 12 h at 80 8C. Conversion to the epoxide functionalities is
completed by treatment with excess sodium hydroxide at 80 8C
over 1 h. The yields of the bis(epoxide)s ranged from 15% to 60%
(Table 1).
Table 1
Characterization data for aromatic bis(epoxide)s
Compound
Aromatic bis(epoxide)s
mp (8C)
Yield (%)
50
5
75.1–76.0
6
Oil
47
7
8
9
129.3–130.8
116.9–117.4
Oil
60
40
25
10
174.2–174.5
15

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X.-S. Huang, F.-L. Qing / Journal of Fluorine Chemistry 129 (2008) 1076–1082
Scheme 2. Synthesis of aromatic bis(epoxide)s 5–10.
Fig. 1. FT-IR spectrum of 11a.
fluorines of trifluoromethyl groups and aromatic ring appeared
at ꢀ63.56 ppm (s, Fa, 6F) and ꢀ115.30 ppm (s, Fb, 2F)
respectively. The molecular weights of the fluorinated polymers
determined by GPC in THF or DMF using polystyrene as standard
are in the range of 32,600–49,100 for Mn and 44,400–62,800 for
Mw with the Mw/Mn values of 1.28–1.60 (Table 2).
Scheme 3. Synthesis of poly(hydroxyether terephthalate)s.
2.4. Hydrogen-bond interactions
(Fig. 2A) of 11a, it can be seen that protons in aromatic ring
appeared at 7.79 ppm (t, H6, 2H), 7.29 ppm (d, H5, 4H), 7.03 ppm
(d, H4, 4H); signals of 4.59–4.49 ppm (m, H1, 4H), 4.41–4.37 ppm
(m, H2, 2H), 4.26–4.18 ppm (m, H3, 4H) belonged to protons in
the aliphatic chain. In 19F NMR spectrum (Fig. 2B), signals of
To investigate whether the fluorine atoms can provide the
additional intermolecular hydrogen bond interactions in the
fluorine-containing poly(hydroxyether terephthalate)s, polymer
11g was synthesized from the polyaddition from terephthalic acid
(TA) and with bis(epoxide) 6 under the same reaction conditions
Fig. 2. 1H NMR (A) and 19F NMR (B) spectra of 11a.

X.-S. Huang, F.-L. Qing / Journal of Fluorine Chemistry 129 (2008) 1076–1082
1079
Table 2
Table 4
Yield and GPC results of polymers 11a–f
Thermal properties of polymers 11a–f
Polymer
Yield
Mn (ꢃ10ꢀ4
)
Mw (ꢃ10ꢀ4
)
Mw/Mn
Polymer
Tg (8C)a
Td (8C)a
T5% (8C)b
T10% (8C)b
Rw (%)c
11aa
11ba
11cb
11da
11ea
11fa
75
71
83
65
73
70
3.26
3.41
4.91
3.54
4.42
3.32
4.60
5.46
6.28
5.51
5.58
4.44
1.41
1.60
1.28
1.55
1.26
1.33
11a
11b
11c
11d
11e
11f
91
66
357
347
355
349
330
348
299
217
334
305
242
321
327
323
351
326
292
335
22
9
55
21
16
14
18
74
69
135
a
a
GPC in THF vs. polystyrene at 35 8C.
GPC in DMF vs. polystyrene at 35 8C.
DSC and TGA at 10 8C/min in N2.
Temperatures at 5% and 10% weight loss.
b
b
c
Residual weight retention at 500 8C.
Table 3
ascribed to the free hydroxyls [22]. It was noted that a new band
at a higher frequency (ꢁ3512 cmꢀ1) is discernable. This showed
that there was the formation of the weaker hydrogen bond –
OHꢂ ꢂ ꢂ–F interactions in 11b.
Solubility of polymers 11a–fa
Polymer Solvent
DMSO DMF MeOH Dioxane THF CHCl3 Acetone Toluene
11a
11b
11c
11d
11e
11f
++
++
++
++
++
++
++
++
++
++
++
++
+
+
+
+
+
+
++
++
++
++
++
++
++
++
ꢀ
+
+
ꢀ
+
+
+
++
++
ꢀ
+
+
ꢀ
+
+
+
2.5. Solubility
The solubility of the resulting polymers 11a–f in a number of
solvents was examined. As summarized in Table 3, all the polymers
were soluble in DMSO, DMF and dioxane while partially soluble or
swelling in methanol. However, polymer 11c was insoluble in THF,
chloroform, acetone and toluene. The results indicated that the
obtained PHETs exhibited good solubility.
++
++
++
++
++
++
a
++, soluble at room temperature; +, partially soluble or swelling; ꢀ, insoluble.
for preparation of polymer 11b. The molecular weight of polymer
11g is 10,700 for Mn and 13,300 for Mw. The investigation of the
hydrogen bond interactions was carried out by comparison the
hydroxyl stretching vibration range of 3700–3000 cmꢀ1 in FT-IR
spectra of polymers 11b and 11g (Fig. 3). The broad bands reflect
the wide distribution of hydrogen-bonded hydroxyl stretching
frequencies. The shoulder bands centered at 3570 cmꢀ1 are
2.6. Thermal properties of polymers
Thermal properties of polymers 11a–f were evaluated by means
of differential scanning calorimetry (DSC) and thermo-gravimetric
analysis (TGA). The results are listed in Table 4. DSC was used to
determine the glass transition temperatures of polymers. All the
samples were first heated up to 150 8C and held for 5 min to
remove thermal history, followed by quenching to ꢀ70 8C. A
heating rate of 10 8C/min in nitrogen was used at all cases. The DSC
curves of 11a–f are presented in Fig. 4. It can be seen that all the
polymers are amorphous thermoplastics with glass transition
temperatures (Tg) of 55–135 8C. As expected, 11f derived from the
relatively rigid naphthyl unit exhibited the highest Tg (135 8C). The
Tg of PHET decreases as the Ar portion of the polymer backbone
becomes more flexible. The Tg of 11a (91 8C) was higher than that
of 11b (66 8C), this might be attributed to the bulky trifluoromethyl
moieties. The TGA curves of polymers 11a–f under nitrogen
atmosphere are given in Fig. 5. The polymers exhibited tempera-
tures corresponding to 5% weight loss ranging from 217 to 334 8C
and 10% weight loss ranging from 292 to 351 8C under nitrogen.
The initial thermal decomposition temperatures (Td) were
Fig. 3. Comparison of FT-IR spectra in the region of 3700–3000 cmꢀ1 for 11b and
11g.
Fig. 4. DSC curves of polymers 11a–f in nitrogen.

1080
X.-S. Huang, F.-L. Qing / Journal of Fluorine Chemistry 129 (2008) 1076–1082
resolution of 2 cmꢀ1 for signal accumulation. Gas chromatogra-
phy/mass spectrometry (GC/MS) was recorded on a Finnigan-MAT-
8430 instrument using EI ionization at 70 eV. 1H NMR (400 MHz)
and 19F NMR (376 MHz) spectra were recorded on a Bruker AM 400
spectrometer system. Chloroform-d, acetone-d6 and dimethyl
sulphoxide-d6 were used as the solvents and chemical shifts
reported were internally referenced to Me4Si (0 ppm) and CFCl3
(0 ppm) for 1H and 19F nuclei. Relative molecular weights and
molecular weight distributions were measured by gel permeation
chromatography (GPC) system equipped with a Waters 1515
Isocratic HPLC pump, a Waters 2414 refractive index detector (RI),
a Waters 2487 dual-wavelength absorbance detector and a set of
Waters Styragel columns (HR3, HR4 and HR5, 7.8 mm ꢃ 300 mm).
GPC measurements were carried out at 35 8C using THF or DMF as
an eluent with a 1.0 mL/min flow rate. The system was calibrated
with polystyrene standards. Differential scanning calorimetry
(DSC) was conducted on a NetZSch (German) DSC 204 F1 system
under nitrogen calibrated with indium and zinc standards. All the
samples were first heated up to 150 8C and held for 5 min to
remove thermal history, followed by quenching to ꢀ70 8C. A
heating rate of 10 8C/min was used at all cases. Dynamic thermo-
gravimetric analysis (TGA) was performed on NetZSch (German)
TGA 209 F1 system on powder samples at a heating rate of 10 8C/
min under nitrogen atmosphere from 25 to 500 8C.
Fig. 5. TGA curves of polymers 11a–f in nitrogen.
determined in the range of 330–357 8C in nitrogen for all polymers
tested. Meanwhile, the residual weight retention at 500 8C was also
summarized in Table 4. It showed that the residual weight of 11a at
500 8C under nitrogen was 22%, much higher than that of 11b (9%),
which indicated that the thermal stability can be improved by the
introduction of trifluoromethyl moieties.
4.3. Synthesis of 2,5-dimethyl-1,4-benzenebis(diazonium)
tetrafluoroborate 1
3. Conclusion
2,5-Dimethyl-1,4-benzenediamine (27.2 g, 0.20 mol) was dis-
solved in 110 mL of 37% hydrochloric acid to form a slurry. With
energetic stirring, one-third of the slurry was first added to 38%
fluoroboric acid (219.2 g, 160 mL, 0.95 mol) at or below ꢀ10 8C.
Sodium nitrite (30.36 g, 0.44 mol) in 50 mL of water was slowly
added to the suspension. Entire amount of the slurry may be added
by the time half of the nitrite has been added. After addition of the
nitrite solution, the mixture was allowed to stir for 45 min with
continued cooling. The resultant precipitate was suction filtered
and washed with cold water (200 mL), cold ethanol (200 mL) and
finally cold ether (300 mL). The obtained beige solid was dried
under high vacuum overnight to give 60.05 g of 1 (90%) with mp
149–151 8C. This material was used directly for the next step
without further purification.
A novel and more reliable synthetic route to 2,5-difluoroter-
ephthalic acid (DFTA) was developed. The polyaddition of DFTA
with various aromatic bis(epoxide)s to produce a series of
poly(hydroxyether terephthalate)s (PHET) in good yields. The
introduction of DFTA may contribute to the formation of additional
hydrogen bond interactions in PHET. The glass transition
temperatures of PHET are also dependent on the aromatic unit
(Ar) used.
4. Experimental
4.1. Materials
Dioxane was freshly distilled under nitrogen over sodium.
2,5-Dimethyl-1,4-benzenediamine was obtained from Zhejiang
Dragon Chemical Co., Ltd. Hexafluorobisphenol A was obtained
from Zigong Longxiang Chemical Co., Ltd and purified by
sublimation. Bisphenol A was obtained from Sinopharm Chemi-
cal Reagent Co., Ltd and recrystallized from toluene. 4,40-
Dihydroxybenzophenone was obtained from Shanghai Dere
Finechem Co., Ltd and recrystallized from acetone. 1,5-Dihy-
droxynaphthalene was obtained from Fluka. Other reagents or
materials were used as received.
4.4. Synthesis of 2,5-difluo-p-xylene 2
Compound 1 (57.30 g, 0.17 mol) was placed in a 500-mL
round-bottom flask connected with two cold traps and a gas
absorption bottle. With low-speed stirring, the flask was care-
fully heated in an oil bath at 80 8C until the gas evolution began. A
small amount of sea sand may be added to avoid vigorous
decomposition. The temperature of the oil bath was gradually
increased to 120 8C to complete the decomposition. Finally, the
black residue was then distilled in steam and extracted with
diethyl ether. The organic layer was washed with 5% sodium
bicarbonate and then dried over anhydrous magnesium sulfate.
After removal of the solvent, the crude product was recrystallized
from hexane. White crystals of compound 2 (17.50 g, 72%) were
4.2. Measurements
Melting point ranges were determined on a WRS-2A capillary
melting point apparatus (uncorrected). Elemental analysis was
carried out on a Carlo-Erba1106 system. The FT-IR measurements
were conducted on a Nicolet 380 FT-IR spectrophotometer at room
temperature. To obtain the FT-IR spectra, the thin films of plain
PHET were cast onto KBr windows from 2 wt.% DMF solution. The
films obtained were further dried in vacuo at 60 8C for 72 h to
remove residual solvent. All of casting films used in the study were
sufficiently thin to be within a range where the Beer–Lambert law
is obeyed. The FT-IR spectra were recorded with 32 scans at a
obtained with mp 39.0–40.2 8C. 1H NMR (400 MHz, CDCl3):
d
6.80
(t, J = 8 Hz, 2H), 2.21 (s, 6H). 19F NMR (376 MHz, CDCl3):
(t, J = 7.52 Hz, 2F).
d
ꢀ124.6
4.5. Synthesis of 1,4-bis(bromomethyl)-2,5-difluorobenzene 3
Following the general procedure of Greenwood et al. [17],
compound 2 (8.55 g, 60 mmol) was dissolved in 100 mL of carbon

X.-S. Huang, F.-L. Qing / Journal of Fluorine Chemistry 129 (2008) 1076–1082
1081
tetrachloride in a 250-mL round-bottom flask equipped with a
condenser. N-Bromosuccinimide (22.43 g, 126 mmol) was added
along with 0.02 g of benzoyl peroxide as an initiator. Under nitrogen
atmosphere, the mixture was heated under reflux with two 275 W
sunlamp placed 5 cm from the reaction flask for 4.5 h, and the
resulting suspension was suction filtered to remove succinimide
byproduct. The solvent was then removed from the filtrate under
reduced pressure, and the crude product was recrystallized from
ethanol to give 15.35 g (85%) of white needle-like crystals as
4.19 (dd, J = 11.2, 3.2 Hz, 2H), 3.91 (dd, J = 11.2, 5.6 Hz, 2H), 3.4–
3.31 (m, 2H), 2.88 (t, J = 4.8 Hz, 2H), 2.73 (t, J = 4.8 Hz, 2H).
Compound 10: IR (
918. 1H NMR (400 MHz, DMSO-d6):
n
max, cmꢀ1, KBr): 1593, 1405, 1267, 1043,
d
7.77 (d, J = 8.4 Hz, 2H), 7.42 (t,
J = 8.0 Hz, 2H), 7.02 (d, J = 7.6 Hz, 2H), 4.50 (dd, J = 11.6, 2.8 Hz, 2H),
4.03 (dd, J = 11.6, 6.4 Hz, 2H), 3.49–3.46 (m, 2H), 2.91 (t, J = 4.8 Hz,
2H), 2.82 (t, J = 4.8 Hz, 2H).
4.8. General procedure for the synthesis of poly(hydroxyether
compound 3 with mp 110–112 8C. 1H NMR (400 MHz, CDCl3):
d
7.13
terephthalate)s 11a–f
(t, J = 7.6 Hz, 2H), 4.44 (s, 4H). 19F NMR (376 MHz, CDCl3):
(t, J = 7.52 Hz, 2F). MS (EI): m/z 300 (M+).
d
ꢀ121.6
Poly(hydroxyether terephthalate)s were prepared by the
polyaddition of 2,5-difluoroterephthalic acid
4 with various
4.6. Synthesis of 2,5-difluoroterephthalic acid (DFTA) 4
aromatic bis(epoxide)s 5–10 under a nitrogen atmosphere. The
following procedure is for the preparation of 11a and is a
representative for the preparation of the rest of the polymers.
Compound 4 (0.202 g, 1 mmol), 5 (0.448 g, 1 mmol) and TBAB
(0.02 g, 0.06 mmol) were dissolved in 2.5 mL of dioxane in a
polymerization tube. The reaction was carried out at 80 8C for 40 h.
After cooling to the room temperature, the mixture was poured
into ethanol/hexane (1/5, v/v, 100 mL) to precipitate a polymer.
It was re-precipitated three times from THF into ethanol/hexane
(1/1) and dried in vacuo at 60 8C for 48 h.
To a mixture of compound 3 (7.50 g, 25 mmol), sodium
periodate (5.35 g, 25 mmol) was added 50 mL of 2% H2SO4. The
reaction mixture was heated at 95 8C for 24 h. It was subsequently
cooled to room temperature, stoppered and placed in a freezer for
several hours. The cold mixture was filtered and the precipitate
was washed with water. The solids were recrystallized from acetic
acid to give 4.04 g (80%) of compound 4 as white crystals with mp
316–319 8C. IR (
(400 MHz, DMSO-d6):
NMR (376 MHz, CDCl3):
n
max, cmꢀ1, KBr): 3427–2512, 1691, 1184. 1H NMR
13.86 (s, COOH), 7.71 (t, J = 8.0 Hz, 2H). 19
d
F
Polymer 11a: IR (
n
max, cmꢀ1, KBr): 1727, 1611, 1513, 1421,
7.79 (t,
d
ꢀ115.81 (t, J = 7.5 Hz, 2F). MS (EI): m/z
1249, 1176, 1109, 1042. 1H NMR (400 MHz, acetone-d6):
d
202 (M+). Anal. Calcd. for C8H4O4F2: C, 47.52%, H, 1.98%. Found: C,
47.80%, H, 2.04%.
J = 7.6 Hz, 2H), 7.29 (d, J = 8.4 Hz, 4H), 7.03 (d, J = 8.8 Hz, 4H), 4.59–
4.49 (m, 4H), 4.41–4.37 (m, 2H), 4.26–4.18 (m, 4H). 19F NMR
(376 MHz, acetone-d6,):
Polymer 11b: IR (
max, cmꢀ1, KBr): 1728, 1606, 1507, 1420,
1256, 1181, 1099,1040,1038. 1H NMR (400 MHz, DMSO-d6):
7.81
d
ꢀ63.56 (s, 6F), ꢀ115.30 (s, 2F).
4.7. General procedure for preparation of bis(epoxide)s 5–10
n
d
Under argon atmosphere, the bisphenol (15 mmol), benzyl-
triethylammonium chloride (0.02 g, 0.09 mmol), and epichlorohy-
drin (30 mL, 35.4 g, 0.38 mol) were heated at 80 8C over 12 h. After
that, a solution of 50% aqueous sodium hydroxide (3.6 g, 45 mmol
NaOH) was added dropwise to the vigorously stirred solution over
1 h. On completion of addition, the mixture was allowed to stir at
this temperature for 4 h. The reaction mixture was then cooled and
poured into methylene chloride (200 mL) and washed with water
(4 ꢃ 100 mL). The organic layer was separated, dried over
magnesium sulfate and filtered to yield a clear filtrate. The solvent
was removed under reduced pressure to yield crude 5–10 as either
an oil or a solid. Bis(epoxide)s 5, 6 and 9 were purified via
chromatography on silica gel using ethyl acetate/petroleum ether
(1/5, v/v) as the eluent. Bis(epoxide)s 7, 8 and 10 were purified by
twice recrystallizations from ethanol.
(t, J = 7.6 Hz, 2H), 7.07 (d, J = 8.2 Hz, 4H), 6.83 (d, J = 8.4 Hz, 4H),
4.41–4.35 (m, 4H), 4.26–4.13 (m, 2H), 4.05–3.95 (m, 4H), 1.55 (s,
6H). 19F NMR (376 MHz, DMSO-d6):
d
ꢀ115.27 (s, 2F).
max, cmꢀ1, KBr): 1724, 1600, 1504, 1421,
1245, 1171, 1108, 1033. 1H NMR (400 MHz, DMSO-d6):
7.89 (t,
Polymer 11c: IR (
n
d
J = 7.6 Hz, 2H), 7.81 (d, J = 6 Hz, 4H), 7.09 (d, J = 8.4 Hz, 4H), 4.47–
4.33 (m, 4H), 4.25–4.18 (m, 2H), 4.18–4.07 (m, 4H). 19F NMR
(376 MHz, DMSO-d6):
Polymer 11d: IR (
max, cmꢀ1, KBr): 1728, 1589, 1506, 1420, 1257,
1181, 1099, 1043. 1H NMR (400 MHz, DMSO-d6):
7.87 (t, J = 7.6 Hz,
2H), 6.88(s, 4H), 4.45–4.29(m, 4H), 4.25–4.08(m, 2H), 3.97–3.91(m,
4H). 19F NMR (376 MHz, DMSO-d6):
ꢀ115.30(s, 2F).
Polymer 11e: IR (
max, cmꢀ1, KBr): 1727, 1596, 1493, 1420,
1257, 1180, 1098, 1047. 1H NMR (400 MHz, DMSO-d6):
7.86(t,
d
ꢀ115.25(s, 2F).
n
d
d
n
d
J = 7.6 Hz, 2H), 7.16 (s, 1H), 6.55–6.52 (m, 3H), 4.47–4.29 (m, 4H),
4.25–4.09 (m, 2H), 4.10–3.92 (s, 4H). 19F NMR (376 MHz, DMSO-
Compound 5: IR (
n
max, cmꢀ1, KBr): 1612, 1260, 1245, 1176, 967.
7.35–7.30 (m, 4H), 6.95–6.92 (m, 4H),
1H NMR (400 MHz, CDCl3):
d
d6):
Polymer 11f: IR (
1261, 1179, 1082. 1H NMR (400 MHz, DMSO-d6):
d
ꢀ115.26 (s, 2F).
4.28 (dd, J = 11.2, 2.8 Hz, 2H), 4.02 (dd, J = 11.2, 5.6 Hz, 2H), 3.41–
3.39 (m, 2H), 2.96 (t, J = 4.8 Hz, 2H), 2.80 (t, J = 4.8 Hz, 2H).
n
max, cmꢀ1, KBr): 1726, 1595, 1506, 1418,
7.85–7.76 (m,
d
Compound 6: IR (
n
max, cmꢀ1, KBr): 1609, 1245, 1035, 1184, 913.
4H), 7.35 (d, J = 6.8 Hz, 2H), 6.98 (s, 2H), 4.55–4.45 (m, 4H), 4.34–
4.22 (m, 2H), 4.19–4.02 (s, 4H). 19F NMR (376 MHz, DMSO-d6):
d
1H NMR (400 MHz, CDCl3):
d
7.15–7.11 (m, 4H), 6.84–6.80 (m, 4H),
4.17 (dd, J = 10.8, 3.2 Hz, 2H), 3.95 (dd, J = 10.8, 5.6 Hz, 2H), 3.34–
3.32 (m, 2H), 2.89 (t, J = 4.4 Hz, 2H), 2.74 (t, J = 4.4 Hz, 2H), 1.63 (s,
6H).
ꢀ115.27 (s, 2F).
Acknowledgments
Compound 7: IR (
n
max, cmꢀ1, KBr): 1641 (C O), 1602, 1252,
7.79–7.75 (m, 4H), 7.02–
1026, 910. 1H NMR (400 MHz, CDCl3):
d
We are grateful to National Natural Science Foundation of
China, the Program for Changjiang Scholars and Innovative
Research Team in University (No. IRT0526) and Shanghai
Municipal Scientific Committee for the financial support.
6.96 (m, 4H), 4.34–4.30 (dd, J = 10.8, 3.2 Hz, 2H), 4.02 (dd, J = 11.2,
5.6 Hz, 2H), 3.40–3.37 (m, 2H), 2.93 (t, J = 4.4 Hz, 2H), 2.78 (t,
J = 4.4 Hz, 2H).
Compound 8: IR (
n
max, cmꢀ1, KBr): 1630, 1498, 1344, 1109, 910.
6.85 (s, 4H), 4.16 (dd, J = 10.8, 3.2 Hz,
1H NMR (400 MHz, CDCl3):
d
References
2H), 3.91 (dd, J = 10.8, 5.6 Hz, 2H), 3.34–3.31 (m, 2H), 2.89 (t,
J = 4.8 Hz, 2H), 2.73 (t, J = 4.8 Hz, 2H).
[1] T. Nishikubo, A. Kameyama, Prog. Polym. Sci. 18 (1993) 963–995.
[2] H. Kudo, T. Nishikubo, J. Polym. Sci. A: Polym. Chem. 45 (2007) 709–726.
[3] M.N. Mang, J.E. White, A.P. Haag, S.L. Kram, C.N. Brown, Polym. Prepr. 36 (1995)
180–181.
Compound 9: IR (
1H NMR (400 MHz, CDCl3):
n
max, cmꢀ1, KBr): 1598, 1490, 1288, 1082, 908.
d
7.19–7.14 (m, 1H), 6.54–6.50 (m, 3H),

1082
X.-S. Huang, F.-L. Qing / Journal of Fluorine Chemistry 129 (2008) 1076–1082
[4] D.L. Rick, J.W. Davis, S.L. Kram, M.N. Mang, T.D. Lickly, J. Environ. Polym. Degrad. 6
(1998) 143–157.
[5] M.N. Mang, J.E. White, S.L. Kram, D.L. Rick, R.E. Bailey, P.E. Swanson, Polym. Mater.
Sci. Eng. 76 (1997) 412–413.
[13] J.L. Willet, W. Doane, US Patent 6,191,196 (2001).
[14] X. Cao, S.H. Gordon, J.L. Willet, D.J. Sessa, Polym. Prepr. 42 (2001) 623–624.
[15] X. Cao, A. Mohamed, S.H. Gordon, J.L. Willet, D.J. Sessa, Thermochim. Acta 406
(2003) 115–127.
[6] R.L. Shogren, W.M. Noane, D. Garlotta, J.W. Lawton, J.L. Willet, Polym. Degrad.
Stab. 79 (2003) 405–411.
[7] J.L. Willet, W.M. Doane, Polymer 43 (2002) 4413–4420.
[8] P.S. Walia, J.W. Lawton, R.L. Shogren, F.C. Felcker, Polymer 41 (2000) 8083–8093.
[9] S.S. Lawrence, J.L. Willet, C.J. Carriere, Polymer 42 (2001) 5643–5650.
[10] G. Zhou, J.L. Willett, C.J. Carriere, Y.V. Wu, J. Polym. Environ. 8 (2000) 145–150.
[11] C. Wang, C.J. Carriere, J.L. Willett, J. Polym. Sci. B: Polym. Phys. 40 (2002) 2324–2332.
[12] X. Cao, S.H. Gordon, J.L. Willet, D.J. Sessa, Polym. Prepr. 42 (2001) 652–653.
[16] B.Q. Liu, W.A. Zhang, S.X. Zheng, Polymer 46 (2005) 10574–10584.
[17] Y. Ye, B. Zhu, Y. Inoue, Prog. Polym. Sci. 29 (2004) 1021–1051.
[18] J.K. Lee, J.H. Kim, Y.J. Kim, Bull. Korean Chem. Soc. 7 (2003) 1029–1031.
[19] P.E. Cassidy, V.S. Reddy, React. Funct. Polym. 30 (1996) 141–147.
[20] T. Kimura, T. Fukuda, H. Matsuda, A. Komoriya, M. Kazama, Polym. Adv. Technol.
12 (2001) 231–236.
[21] D.J. Brennan, J.E. White, C.N. Brown, Macromolecules 31 (1998) 8281–8290.
[22] M.M. Coleman, E.J. Moskala, Polymer 24 (1983) 251–257.