Synthesis of polyfluorinated aromatic polyesters

Article abstract of DOI:10.1016/S0022-1139(99)00245-6

Perfluoroalkylation of phenolic compounds by R_FI/Na₂S₂O₄ reagent system was used to synthesize fluorinated monomers useful in polycondensation reactions. A series of fluorinated aromatic polyesters was prepared

Full text of DOI:10.1016/S0022-1139(99)00245-6

Journal of Fluorine Chemistry 102 (2000) 55±59
Synthesis of poly¯uorinated aromatic polyesters
Li Zhang, Wei-Yuan Huang*
Laboratory of Organo¯uorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China
Received 5 June 1999; received in revised form 29 June 1999; accepted 28 July 1999
Dedicated to Professor Paul Tarrant on the occasion of his 85th birthday
Abstract
Per¯uoroalkylation of phenolic compounds by RFI/Na2S2O4 reagent system was used to synthesize ¯uorinated monomers useful in
polycondensation reactions. A series of ¯uorinated aromatic polyesters was prepared from poly¯uoroalkylated hydroquinone and
terephthalic acid derivatives and some properties of these polymers were discussed. # 2000 Elsevier Science S.A. All rights reserved.
Keywords: Fluorine-containing hydroquinone; Fluorinated aromatic polyester; Polycondensation
1. Introduction
In order to overcome these dif®culties, we have devised
the following structures:
In our systematic study on the application of RFI/Na2S2O4
reagent system in organic synthesis [1], we were interested
in the synthesis of ¯uoroalkylated phenolic compounds to be
used as F-containing monomers in polycondensation reac-
tions. It is well known that phenols can be readily per¯uor-
oalkylated at o-and p-positions in good yields [2],
In these ways we are able to protect the RF group from
the attack by base, i.e., by putting a short chain of several
methylene groups between the phenolic OH or between
the aromatic nucleus and the RF group. For example, we
per¯uoroalkylated p-hydroxybenzoic acid ester under
mild conditions to form the ¯uoroalkylated product, 1,
which was then treated with bromohydrin and NaH to
form the corresponding p-(b-hydroxyethoxy) derivatives,
2 [4],
However, these o- and p-¯uoroalkylated phenols are not
stable under basic conditions. They lose a-F atoms readily to
form the corresponding a-keto derivatives [3],
As the subject of this paper, we also studied the synthesis
of the F-containing phenols, in which a short chain of several
methylene groups were placed between the aromatic nucleus
and the RF group.
* Corresponding author. Tel.: ‡86-21-64163300;
fax: ‡86-21-64166128.
E-mail address: wyhuang@pub.sioc.ac.cn (W.-Y. Huang).
0022-1139/00/$ ± see front matter # 2000 Elsevier Science S.A. All rights reserved.
PII: S 0 0 2 2 - 1 1 3 9 ( 9 9 ) 0 0 2 4 5 - 6

56
L. Zhang, W.-Y. Huang / Journal of Fluorine Chemistry 102 (2000) 55±59
2. Results and discussion
We chose hydroquinone monomethyl ether as the starting
material for the following sequence of reactions:
These polycondensation reactions seems to give good
yields of polymeric products with similar m.w. as shown by
the intrinsic viscosity study of their solutions in conc.
H2SO4.
Preliminary studies on the physicochemical properties of
these F-containing polymers indicated that, in comparison
with the F-free polyesters:
1. None of the F-containing polyesters showed a definite
m.p. and all of them can be casted into films at about
70 ± 1208C lower than that of the F-free polyester.
2. All of them showed better thermal stability.
3. The films of these F-containing polyesters showed
improved water repellency.
Then we studied the synthesis of polyesters from these
¯uoroalkylhydroquinones by reaction with terephthalic acid
derivatives. First, we tried the method developed by Ogata
et al. [5] because the reaction conditions are very mild, i.e.,
using hexachloroethane and PPh3 in pyridine to effect the
esteri®cation.
4. The side chain of these F-containing polymers appeared
to be a weak point during thermal decomposition.
While the reaction of benzoic acid and ¯uorinated mono-
methyl ether proceeded well, the results with terephthalic
acid were not as good, especially in the polycondensation
reaction between terephthalic acid and the hydroquinones.
Further studies on the properties of these polymers are in
progress.
3. Experimental
All melting points and boiling points were uncorrected.
IR spectra were recorded with Schimadzu IR-440 Spectro-
meter, liquid ®lm or KBr pellets for solids were used.
1H NMR spectra were recorded on Varian EM-360A
(60 MHz), FX-90Q (90 MHz) or Bruker AM 300
(300 MHz) spectrometers using TMS as internal standard.
19F NMR spectra were recorded on Varian EM-360L
(56.4 MHz) spectrometer and CF3CO2H was used as exter-
nal standard, dCF CO H ˆ 0:00; positive toward high ®eld.
Only low m.w. telomers were formed and in low yields as
shown in the following equation:
3
2
MS were measured on Finnegan GC-MS 4021 spectrometer.
Silica gel H (size 10±40 m) was used for TLC and column
chromatography.
Solvents and reagents: CP or AR grade reagents were
used. Pyridine was dried over CaH2 and redistilled. Hydro-
quinone, hexachloroethane, triphenylphosphine and ben-
zoic acid were puri®ed by recrystallization from 95%
ethanol. Terephthaloyl chloride was recrystallized from
hot hexane. CHCl2CHCl2 was treated with hot conc.
H2SO4 and then washed with conc. H2SO4 and water
successively, dried over anhydrous K2CO3 overnight and
redistilled, collecting the fraction boiling 145±1468C. N-
methylaniline was redistilled.
The conc. H2SO4 solutions of these polymeric materials
(250 mg/25 ml) were used for viscosity measurement
employing an Ubbelohde viscometer in a thermostat at
308C. Film casting was performed between two pieces of
Al foil under a pressure of 40 KPa for 2 min at the tem-
perature speci®ed (200±3008C). The contact angles (y) were
Finally, by applying the classical Schotten±Baumann
reaction, i.e., by reacting the hydroquinones with terephtha-
loyl chloride in the presence of pyridine, we succeeded in
making a series of polycondensation products as well as
copolycondensation products using a mixture of ¯uorinated
and non¯uorinated hydroquinones. The polycondensation
product of hydroquinone and terephthaloyl chloride was
also prepared under similar condition for comparison in the
preliminary study on the properties of these products.

L. Zhang, W.-Y. Huang / Journal of Fluorine Chemistry 102 (2000) 55±59
57
obtained using ®lms thus obtained and a home-made contact
angle gonimer.
4.69(1H, m, CHI), 6.72(3H, s); 19F NMRꢀCDCl3†, dF(ppm):
3.60(3F, s, CF3), 36.0(2F, t, CH2CF2), 45.3(2F, s), 46.0(4F,
s), 49.0(2F, s); IR(cm 1): 3400(OH), 2920(CH),
1515(ArH), 1200(CF), 1100(CO); Anal.(%) C16H12F13IO2,
Calc.: C, 31.50; H, 1.98; F, 40.49; I, 20.80; Found: C, 31.55;
H, 1.89; F, 40.45; I, 20.44.
5e: Crude yield: quantitative. m.p. 81.0±82.58C.
1H NMRꢀCDCl3†, dH(ppm): 2.82(2H, d-d), 3.15±3.41(2H,
m), 3.81(3H, s), 4.70(1H, m, CHI), 6.73(3H, s);
19F NMRꢀCDCl3†, dF(ppm): 3.20(3F, s, CF3), 35.7(2F, t,
CH2CF2), 44.2(10F, s), 48.8(2F, s); IR(cm 1): 3400(OH),
2920(CH), 1515(ArH), 1200(CF), 1100(CO); Anal.(%)
C18H12F17IO2, Calc.: C, 30.44; H, 1.70; F, 45.49; I,
17.87; Found: C, 30.36; H, 1.51; F, 45.64; I, 15.66.
3.1. Compound 3 and 4 [6]
Hydroquinone monomethyl monoallyl ether, 3, was pre-
pared from the reaction of hydroquinone monomethyl ether
with allyl bromide in acetone in the presence of K2CO3
under re¯ux in 96% yield. The Claisen rearrangement of the
allyl ether to give 4-methoxy-2-allyl phenol (4) was carried
out thermally (2108C) under a N2 atmosphere. The crude
product was distilled under reduced pressure to give 4 with
an yield of 93%, b.p. 958C/0.6 torr.
3.1.1. 2(3'-Perfluoroalkyl-2'-iodopropyl)-4-methoxyphenol
(5a±5e)
Typical procedure: A mixture of 21 g of Na2S2O4
(0.12 mol) and 11 g of NaHCO3 (0.12 mol) was added to
a solution of 15 ml of 4 (0.1 mol), 16 ml of Cl(CF2)2I in
80 ml of CH3CN and 32 ml of H2O with stirring. The whole
mixture was stirred at room temperature and the progress of
the reaction was monitored with 19F NMR until the com-
plete consumption of RFI. Then 200 ml of water was added
and the whole mixture was extracted with ether (3 Â 50 ml),
the organic layer was washed with water and saturated NaCl
solution and dried over anhydrous Na2SO4 overnight. The
solid residue obtained after removal of solvent by distilla-
tion was crystallized from petroleum ether±ethyl acetate
(15:1) to give 22 g of crystalline product, 5a.
3.2. Compounds 6a±6e
There are two typical procedures:
Method A. A solution of 8.4 g 5a (20 mmol) in 50 ml of
ethanol was treated with 8 g (ca. 50 mmol) of activated zinc
and a catalytic amount of acetic acid. The mixture was
re¯uxed for 1.5 h. TLC monitoring indicated that the reac-
tion was complete. The excess zinc was removed by ®ltra-
tion and the residue obtained after the removal of ethanol by
distillation was treated with 50 ml of ether, the ethereal
solution was washed with saturated NaCl solution until
neutral and dried over anhydrous Na2SO4 overnight. The
crude product was crystallized from petroleum ether±ethyl
acetate (15:1) to give colorless platelets of 6a, 4.2 g (yield
70%).
Method B. A mixture of 16.15 g zinc (ca. 0.22 mol) and
80 ml of 10% aqueous HCl was stirred for 2 min, the acidic
solution was decanted and the residual zinc was washed
successively with 2 Â 80 ml acetone, 80 ml ether and acti-
vated by boiling with a mixture 0.538 g AgOAc in 80 ml
HOAc for 1 min. The recovered zinc was washed again with
40 ml HOAc, 4 Â 80 ml ether and 80 ml methanol succes-
sively. The activated zinc thus obtained was allowed to react
with 19 g of 5a (44.5 mmol) in 40 ml methanol. The reac-
tion was complete after stirring for 15 min at room tem-
perature (TLC monitoring). The unreacted zinc was ®ltered
off and the residue obtained after removal of solvent from
the ®ltrate by distillation was dissolved in 250 ml ether. The
ethereal solution was washed successively with 10% aqu-
eous HCl solution, saturated NaCl solution and dried over
anhydrous Na2SO4. The crude product was crystallized
from petroleum ether±ethyl acetate (15:1) to give 11.5 g
of 6a as colorless platelets, yield 86%.
5a: Yield 63% m.p. 85.6±86.58C. 1H NMRꢀCDCl3†,
dH(ppm): 2.85(2H, d-d), 3.20(2H, m), 3.65(3H, s),
4.15(1H, s, OH), 4.63(1H, m, CHI), 6.60(3H, s);
19F NMRꢀCDCl3†, dF(ppm):
6.20(2F, s, CF2Cl),
35.3(2F, t, CH2CF2); IR(cm 1): 3400(OH), 2920(CH),
1515(ArH), 1200(CF), 1100(CO); UV(nm): 298.0(0.230),
204(0.924); Anal.(%) C12H12ClF4IO2, Calc.: C, 33.79; H,
2.84; Cl, 8.31; F, 17.81; I, 29.75; Found: C, 33.92; H, 2.60;
Cl, 8.37; F, 18.03; I, 29.97.
5b: Yield 70%. m.p. 83.0±83.58C. 1H NMRꢀCDCl3†,
dH(ppm): 2.80(2H, d-d), 3.28(2H, m), 3.79(3H, s),
3.93(1H, s, OH), 4.70(1H, m, CHI), 6.71(3H, s);
19F NMRꢀCDCl3†, dF(ppm):
9.98(2F, t, CF2Cl),
35.8(2F, t, CH2CF2), 42.6(2F, s), 45.6(2F, s); IR(cm 1):
3400(OH), 2920(CH), 1515(ArH), 1195(CF), 1100(CO);
Anal.(%) C14H12ClF8IO2, Calc.: C, 31.87; H, 2.29; F,
28.81; Found: C, 31.41; H, 1.85; F, 28.90.
5c: Yield 75%. m.p. 82.0±83.08C. 1H NMRꢀCDCl3†,
dH(ppm): 2.81(2H, d-d), 3.06±3.20(2H, m), 3.80(3H, s),
4.70(1H, m, CHI), 6.72(3H, S); 19F NMRꢀCDCl3†,
dF(ppm):
9.60(2F, t, CF2Cl), 35.6(2F, t, CH2CF2),
6a: m.p. 95.0±95.58C. 1H NMRꢀCDCl3†, dH(ppm): 1.73±
2.26(4H, m), 2.76(2H, t), 3.76(3H, s), 4.14±4.64(1H, broad,
s), 6.68(3H, s); 19F NMRꢀCDCl3†, dF(ppm): 6.5(2F, s,
CF2Cl), 36.3(2F, t, CH2CF2); IR(cm 1): 3320(OH),
2900(CH), 1500(ArH), 1200(CF), 1085(CO); Anal.(%)
C12H13ClF4O2, Calc.: C, 47.94; H, 4.36; Cl, 11.29; F,
25.26; Found: C, 47.92; H, 4.35; Cl, 11.48; F, 25.53.
42.6(2F, s), 44.0(4F, s), 45.6(2F, s); IR(cm 1): 3400(OH),
2920(CH), 1515(ArH), 1200(CF), 1100(CO); Anal.(%)
C16H12ClF12IO2, Calc.: C, 30.67; H, 1.93; Cl, 5.66; F,
36.38; Found: C, 30.73; H, 1.85; Cl, 5.41; F, 36.39.
5d: Yield 66%. m.p. 73.0±74.08C. 1H NMRꢀCDCl3†,
dH(ppm): 2.80(2H, d-d), 3.19±3.32(2H, m), 3.79(3H, s),

58
L. Zhang, W.-Y. Huang / Journal of Fluorine Chemistry 102 (2000) 55±59
6b: Yield 68% (Method A), m.p. 71.5±72.58C.
CF2Cl), 36.6(2F, t, CH2CF2), 42.3(2F, s), 45.2(2F, s);
IR(cm 1): 3350(OH), 2900(CH), 1450(ArH), 1200(CF);
MS(m/z): 386(M ), 123; Anal.(%) C13H11ClF8O2, Calc.:
C, 40.38; H, 2.87; F, 39.31; Found: C, 40.43; H, 2.84; F,
1H NMRꢀCDCl3†, dH(ppm): 1.92±2.06(4H, m), 2.68(2H,
t), 3.77(3H, s), 4.30(1H, s), 6.66(3H, s); 19F NMRꢀCDCl3†,
dF(ppm): 9.5(2F, t, CF2Cl), 36.8(2F, t, CH2CF2), 42.5(2F,
s), 45.5(2F, s); IR(cm 1): 3350(OH), 2900(CH),
1510(ArH), 1200(CF), 1085(CO); Anal.(%) C14H13ClF8O2,
Calc.: C, 41.97; H, 3.27; F, 37.93; Found: C, 41.81; H, 2.99;
F, 38.32.6c: Yield 60% (Method A), m.p. 85.0±86.08C.
1H NMRꢀCDCl3†, dH(ppm): 1.93±2.45(4H, m), 2.68(2H,
t), 3.73(3H, s), 3.9(1H, s), 6.60(3H, s); 19F NMRꢀCDCl3†,
dF(ppm): 9.3(2F, t, CF2Cl), 36.3(2F, t, CH2CF2), 42.6(2F,
s), 44.1(4F, s), 46.0(2F, s); IR(cm 1): 3350(OH), 2900(CH),
‡
40.00.
7c: Yield 91%, m.p. 97.5±98.08C. 1H NMRꢀCDCl3†,
dH(ppm): 1.92±2.15(4H, m), 2.76(2H, m), 4.70(2H, OH),
9.9(2F, t,
6.62(3H, s); 19F NMRꢀCDCl3†, dF(ppm):
CF2Cl), 36.2(2F, t, CH2CF2), 42.2±43.5(6F, m), 45.6(2F,
s); IR(cm 1): 3280(OH), 2900(CH), 1460(ArH), 1200(CF);
‡
MS(m/z): 486(M ), 123; Anal.(%) C15H11ClF12O2, Calc.:
C, 37.02; H, 2.28; F, 46.84; Found: C, 36.91; H, 1.95; F,
1510(ArH),
1200(CF),
1085(CO);
Anal.(%)
46.75.
C16H13ClF12O2, Calc.: C, 38.38; H, 2.62; F, 45.53; Found:
C, 38.37; H, 2.38; F, 45.38.
7d: Yield 90%, m.p. 95.5±96.58C. 1H NMR‰ꢀCD3†2COŠ,
dH(ppm): 1.52(4H, m), 2.15(2H, m), 2.82(2H, OH), 5.96±
6.26(3H, m); 19F NMR‰ꢀCD3†2COŠ, dF(ppm): 4.6(3F, t,
CF3), 37.5(2F, t, CH2CF2), 45.5±46.5(6F, m), 49.6(2F, s);
IR(cm 1): 3250(OH), 2900(CH), 1460(ArH), 1200(CF);
MS(m/z): 440, 268, 123; Anal.(%) C15H11F13O2, Calc.:
C, 38.31; H, 2.36; F, 52.52; Found: C, 38.20; H, 2.26; F,
52.98.
6d: Yield 59% (Method A), m.p. 72.0±73.08C.
1H NMRꢀCDCl3†, dH(ppm): 2.00(4H, m), 2.67(2H, t),
3.73(4H, s), 6.59(3H, s); 19F NMRꢀCDCl3†, dF(ppm):
3.6(3F, t, CF3), 36.9(2F, t, CH2CF2), 44.7±46.0(6F, s),
49.0(2F, s); IR(cm 1): 3380(OH), 2900(CH), 1500(ArH),
1200(CF), 1075(CO); Anal.(%) C16H13F13O2, Calc.: C,
39.68; H, 2.71; F, 51.00; Found: C, 39.38; H, 2.56; F, 51.47.
6e: Yield 85% (Method A), m.p. 85.0±86.08C.
1H NMRꢀCDCl3†, dH(ppm): 1.88±2.21(4H, m), 2.66(2H,
t), 3.77(3H, s), 3.89(1H, s), 6.67(3H, s); 19F NMRꢀCDCl3†,
dF(ppm): 3.3(3F, s, CF3), 36.6(2F, s, CH2CF2), 45.3(10F, s),
48.5(2F, s); IR(cm 1): 3380(OH), 2900(CH), 1500(ArH),
1200(CF), 1040(CO); Anal.(%) C18H13F17O2, Calc.: C,
37.00; H, 2.24; F, 55.28; Found: C, 36.49; H, 1.95; F, 55.76.
7e:Yield85%,m.p.117.5±118.08C.1H NMR‰ꢀCD3†2COŠ,
dH(ppm): 1.54(4H, m), 2.16(2H, m), 2.76(2H, OH),
6.13(3H, m); 19F NMR‰ꢀCD3†2COŠ, dF(ppm): 4.8(3F, t,
CF3), 37.8(2F, t, CH2CF2), 45.5 (10F, m), 49.8(2F, s);
IR(cm 1): 3300(OH), 2900(CH), 1460(ArH), 1200(CF);
Anal.(%) C17H11F17O2, Calc.: C, 35.81; H, 1.79; F,
56.64; Found: C, 35.65; H, 1.80; F, 56.82.
3.4. Polymerization study
3.3. Monomer 7a±7e
3.4.1. Compound 8
Typical procedure: A solution of 30 ml BBr3 in 20 ml of
methylene chloride was added dropwise to a solution of
4.4 g 6a (14.6 mmol) in 30 ml of methylene chloride with
stirring under N2 atmosphere. The mixture was stirred for
3 h at room temperature. TLC monitoring indicated that the
reaction was complete. Methanol (30 ml) was then added
dropwise to the reaction mixture with stirring. 50 ml of
water was added and the whole mixture was neutralized
with Na2CO3 solution, and then extracted with ether
(2 Â 100 ml). The organic layer was washed with saturated
NaCl solution and dried over anhydrous Na2SO4. The
residue obtained after removal of solvent was chromato-
graphed and eluted with petroleum ether±ethyl acetate (12:1
to 4:1) to obtain 4.15 g of the product 7a (yield 98%) as
white solid. m.p. 61.0±62.08C. 1H NMRꢀCDCl3†, dH(ppm):
1.89±2.13(4H, m), 2.63(2H, t), 4.56(2H, OH), 6.60(3H, s);
19F NMRꢀCDCl3†, dF(ppm): 6.6(2F, s, CF2Cl), 36.3(2F, t,
Hexachloroethane (750 mg, 3 mmol) was added to a
solution of 122 mg of benzoic acid (1 mmol), 300 mg of
6a (1 mmol) and 630 mg of triphenylphosphine (2.4 mmol)
in 5 ml of pyridine at room temperature with stirring. An
exothermic reaction started within 1 min and the whole
mixture turned turbid gradually. The stirring was continued
for 50 h, and the resulting mixture was treated with water
and extracted with ether. The ethereal solution was washed
with 1 N HCl, saturated NaCl solution successively, and
dried over anhydrous Na2SO4. The crude product was
chromatographed and eluted with petroleum ether±ethyl
acetate (10:1) to give 280 mg of 8 as a colorless liquid
(yield 77%). 1H NMRꢀCDCl3†, dH(ppm): 1.39±1.51(4H,
m), 2.10(2H, t), 3.25(3H, s), 6.31(2H, m), 7.02(4H, m),
7.69(2H, d); 19F NMRꢀCDCl3†, dF(ppm): 6.30(2F, s),
36.7(2F, t).
CH2CF2); IR(cm 1): 3300(OH), 2900(CH), 1500(ArH),
3.5. Polycondensation of terephthalic acid with
hydroquinone
‡
1200(CF);
MS(m/z):
286(M ),
123;
Anal.(%)
C11H11ClF4O2, Calc.: C, 46.09; H, 3.87; Cl, 12.37; F,
26.51; Found: C, 46.04; H, 3.83; Cl, 12.35; F, 26.55.
7b: Yield 91%, m.p. 65.0±66.58C. 1H NMRꢀCDCl3†,
dH(ppm): 1.90±2.20(4H, m), 2.70(2H, m), 4.70(2H, OH),
A solution of 220 mg of hydroquinone (2 mmol) and
1.5 g of C2Cl6 in 5 ml of pyridine was added dropwise to
a solution of 330 mg of terephthalic acid (2 mmol) and
1.26 g of triphenylphosphine (4.8 mmol) in 5 ml pyridine at
6.63(3H, s); 19F NMRꢀCDCl3†, dF(ppm):
9.6(2F, s,

L. Zhang, W.-Y. Huang / Journal of Fluorine Chemistry 102 (2000) 55±59
59
room temperature with stirring. The mixture soon turned
turbid and the stirring was continued for 5 h. The resulting
mixture was poured into 200 ml methanol and the precipi-
tate was ®ltered and washed with several portions of
methanol and water successively, and then dried to give
144 mg of crude solid product. GPC analysis indicated that
the part soluble in THF was a mixture of oligomers, 9, with
an average m.w. of 600.
quinone (1.5 mmol) in 15 ml of CHCl2CHCl2 by treating
with 2 ml of pyridine and stirring the resulting mixture for
24 h at room temperature. Workup in the usual way gave
copolymer 11a, 1.03 g (yield 80%). Anal.(%),
(C33H21ClF4O8)n, Calc.: C, 60.33; H, 3.22; F, 11.57; Found:
C, 60.03; H, 2.91; F, 9.55. Z(dl/g), 0.4631; y(8), 41.88.
11b: Yield 90%. Anal.(%), (C35H21ClF8O8)n, Calc.: C,
55.53; H, 2.80; F, 20.08; Found: C, 53.94; H, 2.62; F, 20.14.
Z(dl/g), 0.4820; y(8), 54.41.
3.6. Polymers 10a±10e
11c: Yield 87%. Anal.(%), (C37H21ClF12O8)n, Calc.: C,
51.86; H, 2.47; F, 26.60; Found: C, 52.52; H, 2.43; F, 23.48.
Z(dl/g), 0.4632; y(8), 51.42.
11d: Yield 76%. Anal.(%), (C37H21F13O8)n, Calc.: C,
52.87; H, 2.52; F, 29.38; Found: C, 52.55; H, 2.58; F,
29.17. Z(dl/g), 0.3909; y(8), 53.34.
11e: Yield 75%. Anal.(%), (C39H21F17O8)n, Calc.: F,
34.34; Found: F, 33.91. Z(dl/g), 0.3735; y(8), 54.22.
12a: Yield 78%. Anal.(%), (C47H29ClF4O12)n, Calc.: F,
8.47; Found: F, 7.99. Z(dl/g), 0.4583; y(8), 32.15.
12c: Yield 95%. Anal.(%), (C51H29ClF12O12)n, Calc.: F,
20.78; Found: F, 19.84. Z(dl/g), 0.4581; y(8), 43.12.12d:
Yield 93%. Anal.(%), (C51H29F13O12)n, Calc.: F, 22.85;
Found: F, 21.44. Z(dl/g), 0.3836; y(8), 54.66.12e: Yield
92%. Anal.(%), (C53H29F17O12)n, Calc.: F, 27.35; Found:
F, 27.10. Z(dl/g), 0.3663; y(8), 51.30.
Typical procedure: A mixture of 670 mg of terephthaloyl
chloride (3.3 mmol), 860 mg 7a (3 mmol) and 15 ml
CHCl2CHCl2 was stirred under a N2 atmosphere in a three
necked round bottom bottle to give a clear solution. To the
solution 2 ml of pyridine was added dropwise and the
stirring was continued for 24 h, and then diluted with
15 ml of CHCl2CHCl2. The whole mixture was added to
300 ml of methanol with stirring. The precipitate was
collected by ®ltration and washed twice with methanol.
The crude product was triturated with aqueous methanol 2±
3 times, ®ltered and the solid was washed with methanol
twice. The product was dried to constant weight under
reduced pressure to give white polymeric product 10a,
1.16 g (93% yield). Anal.(%), (C19H13ClF4O4)n, Calc.: C,
54.76; H, 3.14; F, 18.23; Found: C, 54.88; H, 2.86; F, 17.94.
Z(dl/g), 0.3601; y(8), 39.83.
10b: Yield 97%. Anal.(%), (C21H13ClF8O4)n, Calc.: C,
48.81; H, 2.54; F, 29.41; Found: C, 49.36; H, 2.27; F, 29.47.
Z(dl/g), 0.4696; y(8), 43.13.
10c: Yield 84%. Anal.(%), (C23H13ClF12O4)n, Calc.: C,
44.79; H, 2.12; F, 36.96; Found: C, 45.04; H, 1.93; F, 34.70.
Z(dl/g), 0.4632; y(8), 50.99.
Acknowledgements
We are grateful for the partial ®nancial support of
National Natural Science Foundation, Grant approval num-
bers 29472074 and 29632003.
10d: Yield 88%. Anal.(%), (C23H13F13O4)n, Calc.: C,
46.02; H, 2.18; F, 41.14; Found: C, 45.93; H, 1.88; F,
40.56. Z(dl/g), 0.3909; y(8), 56.86.
References
10e: Yield 76%. Anal.(%), (C25H13F17O4)n, Calc.: C,
42.88; H, 1.87; F, 46.12; Found: C, 42.86; H, 1.78; F,
45.97. Z(dl/g), 0.3735; y(8), 60.57.
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3.7. Copolycondensation
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989.
Typical Procedure: Copolymer 11a was prepared from a
warm solution of 670 mg of terephthaloyl chloride
(3.3 mmol), 430 mg of 7a (1.5 mmol) and 165 mg of hydro-
[6] W.N. White, D. Gwynn, R. Schlitt, C. Girard, W. Fife, J. Am. Chem.
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