Macromolecules, Vol. 37, No. 15, 2004
Polyester(arylene ether)s 5579
sodium with benzophenone as the indicator. Methylene chlo-
ride was distilled over P2O5. The intermediate 4-bromophenyl
trifluorovinyl ether was synthesized by using a modified
procedure to a published method.11 Intermediates, 2,4,6-
trichloro-1,3,5-trihydroxybenzene, and 2,4,6-tribromo-1,3,5-
trihydroxybenzene were synthesized from procedures used by
Kajigaeshi et al.12 4-(Dimethylamino)pyridinium 4-toluene-
sulfonate (DPTS),13a nonafluoropentyl-1-phenyl-1,1-bisphenol,13b
and tris[(4-trifluorovinyloxy)phenyl]triazine monomer 810 were
prepared according to the reported procedures.
) 109.9 Hz). Anal. Calcd for C28H12F22O6: C, 39.00; H, 1.40.
Found: C, 38.77; H, 1.25. ESI-MS (m/z): calcd 862.0; found
862.1.
Tetr a flu or o-1,4-p h en yl Bis(tr iflu or ovin yloxyben zoa te)
(2). To a 100 mL three-neck round-bottom flask, tetrafluoro-
hydroquinone (0.55 g, 3.0 mmol), 4-trifluorovinyloxybenzoic
acid (1.37 g, 6.3 mmol), DPTS (0.40 g, 1.35 mmol), and dry
methylene chloride (20 mL) were added and placed under a
nitrogen atmosphere. After partial dissolution of the starting
materials, DCC (1.36 g, 6.6 mol) was added to the solution
and stirred for 1 h. Excess DCC (0.12 g, 0.6 mmol) was added
to the solution and allowed to stir for 24 h. The solution was
then filtered and rinsed with methylene chloride. The filtrate
was collected and dried over sodium sulfate. The solvent was
removed to produce a yellowish-white solid. The crude product
was purified over silica gel with hexane-methylene chloride
(4:1) as the eluent to afford a yellowish-white solid (0.49 g,
1H NMR spectra (200 MHz) were taken on a Bruker-200
FT NMR spectrometer, and 19F NMR spectra were recorded
on a Bruker AF 300 spectrometer. Elemental analysis was
taken at QTI (Whitehouse, NJ ). ESI-MS spectra were obtained
on a Bruker Daltonics Esquire ion trap mass spectrometer.
Thermal analyses were performed on a TA Instruments 2010
differential scanning calorimeter (DSC) at a scan rate of 10
°C/min and a Hi-Res TGA 2950 thermogravimetric analyzer
(TGA) at a scan rate of 10 °C/min, under a nitrogen atmo-
sphere. Gel permeation chromatography (GPC) was run
through a Waters 515 HPLC pump in conjunction with a
Waters Styragel 7.8 × 300 mm column and a Waters 410
differential refractometer with THF as the solvent and cali-
brated using polystyrene samples of a known molecular
weight. All surface imaging was conducted in the tapping mode
on a digital multimode Nanoscope III scanning force micro-
scope, with 500 × 500 data acquisitions at a scan speed of 1.4
Hz in air at room temperature. Oxide-sharpened silicon nitride
tips with integrated cantilevers of the nominal spring constant
of 0.38 N/m were used. The refractive indices and birefringence
of the polymer films were measured using a Metricon model
2010 prism coupler. The photothermal deflection spectroscopy
(PDS) experimental test bed of this study used a 1 kW Hg(Xe)
dc short arc lamp as the broadband illumination source at 12.6
Hz chopping frequency, with a 1/8 m dual-grating monochro-
mator. The probe beam was a 10 mW CW He-Ne laser,
attenuated to ∼1.5 mW.
1
28%). H NMR (200 MHz, CDCl3, TMS): δ 7.27 (4 H, d, J )
8.79 Hz), 8.23 (4 H, d, J ) 8.79 Hz). 19F NMR (300 MHz, CDCl3,
C6F6): δ 19.86 (4 F, s), 37.56 (2 F, dd, cis-CFdCF2, Fc), 47.22
(2 F, dd, trans-CFdCF2, Fb), 54.83 (2 F, dd, CFdCF2, Fa), (J ab
) 91.7 Hz, J ac ) 61.0 Hz, J bc ) 109.9 Hz). Anal. Calcd for
C
24H8F10O6: C, 49.50; H, 1.38. Found: C, 49.39; H, 1.28. ESI-
MS (m/z): calcd 582.0; found 582.2.
H exa flu or op r op yl-2,2-d ip h en yl Bis(4-t r iflu or ovin y-
loxyben zoa te) (3). To a 100 mL three-neck round-bottom
flask, hexafluoropropylbisphenol (1.01 g, 3.0 mmol), 4-trifluo-
rovinyloxybenzoic acid (1.37 g, 6.3 mmol), DPTS (0.40 g, 1.35
mmol), and dry methylene chloride (20 mL) were added and
placed under a nitrogen atmosphere. After partial dissolution
of the starting materials, DCC (1.36 g, 6.6 mmol) was added
to the solution and stirred for 1 h. Excess DCC (0.12 g, 0.6
mmol) was added to the solution and allowed to stir for 24 h.
The solution was then filtered and rinsed with methylene
chloride. The filtrate was collected and dried over sodium
sulfate. The solvent was removed to produce a white solid. The
crude product was purified over silica gel with hexane-
methylene chloride (1:1) as the eluent to afford a white solid
4-Tr iflu or ovin yloxyben zoic Acid . To a 300 mL three-
neck round-bottom flask, 4-bromophenyl trifluorovinyl ether
(12.10 g, 48.0 mmol) and dry diethyl ether (60 mL) were added
and placed under a nitrogen atmosphere. The solution was
then cooled to -78 °C. tert-Butyllithium (29 mL, 1.7 M in
pentane) was added dropwise to the solution and allowed to
stir for 1 h. A stream of dry CO2 was introduced into the
solution and stirred at -78 °C for 45 min. The solution was
warmed to room temperature for 30 min and acidified with
an HCl solution (230 mL, 1.5 M). The white precipitate was
collected, washed with H2O and hexane, and dried in a vacuum
oven to afford a white solid (6.57 g, 63%). 1H NMR (200 MHz,
CDCl3): δ 7.17 (2H, d, J ) 8.79 Hz), 8.14 (2H, d, J ) 8.78 Hz).
19F NMR (300 MHz, CDCl3, C6F6): δ 38.00 (1F, dd, cis-
CFdCFFc, Fc), 47.66 (1F, dd, trans-CFdCFFb, Fb), 54.10 (1F,
dd, CFa ) CF2, Fa), (J ab ) 91.5 Hz, J ac ) 61.0 Hz, J bc ) 109.9
Hz). Anal. Calcd for C9H5F3O3: C, 49.56; H, 2.31. Found: C,
49.39; H, 2.20. ESI-MS (m/z): calcd 218.0; found 218.1.
1H,1H,10H,10H-P er flu or o-1,10-d ecyl Bis(4-tr iflu or ovi-
n yloxyben zoa te) (1). To a 100 mL three-neck round-bottom
flask, 1H,1H,10H,10H-perfluoro-1,10-decanediol (1.39 g, 3.0
mmol), 4-trifluorovinyloxybenzoic acid (1.37 g, 6.3 mmol),
DPTS (0.40 g, 1.35 mmol), and dry methylene chloride (20 mL)
were added and placed under a nitrogen atmosphere. After
partial dissolution of the starting materials, N,N′-dicyclohexy-
lcarbodiimide (DCC) (1.36 g, 6.6 mmol) was added to the
solution and stirred for 1 h. Excess DCC (0.12 g, 0.6 mmol)
was added to the solution and allowed to stir for 24 h. The
solution was then filtered and rinsed with methylene chloride.
The filtrate was collected and dried over sodium sulfate. The
solvent was removed to produce a white solid. The crude
product was purified over silica gel with hexane-methylene
chloride (1:1) as the eluent to afford a white solid (2.25 g, 87%).
1H NMR (200 MHz, CDCl3, TMS): δ 4.76 (4 H, t, J ) 13.3
Hz), 7.15 (4 H, d, J ) 8.79 Hz), 8.10 (4 H, d, J ) 8.79 Hz). 19F
NMR (300 MHz, CDCl3, C6F6): δ 38.06 (2 F, dd, cis-CFdCF2,
Fc), 47.42 (2 F, dd, trans-CFdCF2, Fb), 49.00-53.00 (16 F, m),
53.60 (2 F, dd, CFdCF2, Fa), (J ab ) 91.3 Hz, J ac ) 68.5 Hz, J bc
1
(1.83 g, 83%). H NMR (200 MHz, CDCl3, TMS): δ 7.22 (4 H,
d, J ) 8.79 Hz), 7.26 (4 H, d, J ) 8.79 Hz), 7.49 (4 H, d, J )
8.79 Hz), 8.23 (4 H, d, J ) 8.79 Hz). 19F NMR (300 MHz, CDCl3,
C6F6): δ -68.08 (6 F, s), 37.93 (2 F, dd, cis-CFdCF2, Fc), 47.40
(2 F, dd, trans-CFdCF2, Fb), 54.21 (3 F, dd, CFdCF2, Fa), (J ab
) 91.6 Hz, J ac ) 61.0 Hz, J bc ) 109.9 Hz). Anal. Calcd for
C
33H16F12O6: C, 53.82; H, 2.19. Found: C, 53.70; H, 2.11. ESI-
MS (m/z): calcd 736.1; found 736.0.
Non a flu or op en tyl-1,1,1-tr ip h en yl Bis(4-tr iflu or ovin y-
loxyben zoa te) (4). To a 100 mL three-neck round-bottom
flask, nonafluoropentyl-1-phenyl-1,1-bisphenol (1.48 g, 3.0
mmol), 4-trifluorovinyloxybenzoic acid (1.37 g, 6.3 mmol),
DPTS (0.40 g, 1.35 mmol), and dry methylene chloride (20 mL)
were added and placed under a nitrogen atmosphere. After
partial dissolution of the starting materials, DCC (1.36 g, 6.6
mmol) was added to the solution and stirred for 1 h. Excess
DCC (0.12 g, 0.6 mmol) was added to the solution and allowed
to stir for 24 h. The solution was then filtered and rinsed with
methylene chloride. The filtrate was collected and dried over
sodium sulfate. The solvent was removed to produce a white
solid. The crude product was purified over silica gel with
hexane-methylene chloride (1:1) as the eluent to afford a clear
yellowish-brown solid (2.18 g, 81%). 1H NMR (200 MHz, CDCl3,
TMS): δ 7.19 (4 H, d, J ) 8.96 Hz), 7.20 (4 H, d, J ) 8.78 Hz),
7.32 (9 H, m), 8.20 (4 H, d, J ) 8.78 Hz). 19F NMR (300 MHz,
CDCl3, C6F6): δ -117.00 to -84.00 (9 F, m), 37.98 (2 F, dd,
cis-CFdCF2, Fc), 47.68 (2 F, dd, trans-CFdCF2, Fb), 54.36 (2
F, dd, CFdCF2, Fa), (J ab ) 97.7 Hz, J ac ) 61.0 Hz, J bc ) 109.9
Hz). Anal. Calcd for C41H21F15O6: C, 55.05; H, 2.37. Found:
C, 54.92; H, 2.30. ESI-MS (m/z): calcd 894.1; found 894.0.
2,4,6-Tr ich lor o-1,3,5-p h en yl Tr is(t r iflu or ovin yloxy-
ben zoa te) (5). To a 100 mL three-neck round-bottom flask,
2,4,6-trichloro-1,3,5-trihydroxybenzene (0.83 g, 3.6 mmol),
4-trifluorovinyloxybenzoic acid (2.51 g, 11.5 mmol), DPTS (0.71
g, 2.4 mmol), and dry methylene chloride (20 mL) were added
and placed under a nitrogen atmosphere. After partial dis-
solution of the starting materials, DCC (2.67 g, 13.0 mmol)