M. Naritomi et al.
Bull. Chem. Soc. Jpn., 77, No. 11 (2004) 2123
Perfluoro-(2-phenylnaphthalene) (5): Mg (8 g), I2 (0.05 g),
and tetrahydrofuran (1 L) were placed in a 2 L flask. Bromopen-
tafluorobenzene (82 g) was added in the flask at 5–20 C for 1 h
Sb2(C6F4)3 (10):15 Powdered antimony (3 g) and 1,2-diiodo-
tetrafluorobenzene (3 g) were heated together in a sealed tube at
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250 C for 24 h. The tube was cut open and the solid product
(
(
Solution A). Perfluoronaphthalene (45 g) and tetrahydrofuran
500 mL) were placed in another flask. Solution A was added in
was crushed to a powder before being extracted with ether. The
solution was filtered and the ether was removed to give a solid.
After the fractional vacuum sublimation, Sb2(C6F4)3 was ob-
tained. It was recrystallized from hexane. The yield was 21%. It
was identified by GC mass spectrometry (a parent ion peak at
m=z ¼ 686 with a cracking pattern consistent with the objective
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the mixture and heated at 65 C for 8 h. 2M HCl water (600
mL) was added and the precipitated solid was washed with water,
and dried. The solid was subjected to fractional vacuum sublima-
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tion. At 150 C perfluoro-(2-phenylnaphthalene) was obtained.
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The yields were 15%. The material was identified by GC mass
spectrometry (parent ion peaks at m=z ¼ 420 with a cracking pat-
tern consistent with the objective structure). GC purity 99.2%.
structure). GC purity 98.5%. Mp. 268 C.
Perfluoro(tetraphenyl) Tin (11):16 Mg (2.5 g), I2 (0.01 g),
and tetrahydrofuran (200 mL) were placed in a 500 mL flask. Bro-
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Mp. 89 C.
mopentafluorobenzene (25 g) was added in the flask at 5–20 C
for 1 h. Anhydrous tin tetrachloride (26 g) was added to the mix-
Perfluoro-p-terphenyl (6):11 Mg (36.5 g) and tetrahydrofuran
800 mL) were placed in a 2 L flask. Bromopentafluorobenzene
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(
(
ture and the combination was heated at 65 C for 10 h. 2M HCl
370 g) was slowly added in the flask, and the solution was stirred
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aqueous solution (100 mL) was added and the precipitated solid
was washed with water, and dried. The solid was recrystallized
from chloroform; perfluoro(tetraphenyl) tin was obtained in 56%
yield. The material was identified by GC mass spectrometry (a pa-
rent ion peak at m=z ¼ 787 with a cracking pattern consistent with
at 30 C for 6 h (Solution B). Perfluorobiphenyl (334 g) and tet-
rahydrofuran (2 L) were put in another 5 L flask. Solution B
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was added in the flask at 15 C for 1 h and stirred at 30 C for
0 h. The mixture was poured into water, and the precipitated sol-
id was washed with water and dried. The obtained solid was sub-
2
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the objective structure). GC purity 99.2%. Mp. 221 C.
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2,4,6-Tris(pentafluorophenyl)-1,3,5-triazine (13):17 Penta-
fluorobenzonitrile (150 g) and fluorosulfuric acid (500 g) were
placed in a 1 L glass flask with stirring at room temperature for
7 days. The mixture was poured into cold water with ice (3 L)
and the precipitated solid (132 g) collected, washed with water,
and dried. The solid was recrystallized twice from toluene.
2,4,6-Tris(pentafluorophenyl)-1,3,5-triazine was obtained as a
white crystal in 46% yield. The material was identified by GC
mass spectrometry (a parent ion peak at m=z ¼ 579 with a crack-
ing pattern consistent with the objective structure). GC purity
jected to fractional vacuum sublimation. At 140 C, perfluoroter-
phenyl was obtained as white crystals in 10% yield. The material
was identified by GC mass spectrometry (a parent ion peak at
m=z ¼ 482 with a cracking pattern consistent with the objective
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structure). GC purity 99.8%. Mp. 194 C.
Perfluorotriphenylene (7):12
10 g) and copper powder (10 g) were heated at 200 C for 50
1,2-Diiodotetrafluorobenzene
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(
h in a sealed evacuated tube. The contents were then extracted
with ether, the solution was filtered and the ether was removed
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at 0 C to give a solid that was subjected to fractional vacuum sub-
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limation. Dodecafluorotriphenylene sublimed at 140 C and was
99.8%. Mp. 123 C.
0
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0
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0
recrystallized from hexane. The yields were 18%. The material
was identified by GC mass spectrometry (parent ion peaks at
m=z ¼ 444 with a cracking pattern consistent with the objective
2,4,6-Tris(2 ,3 -dichloro-1 ,1 ,2 ,3 ,3 -pentafluoropropyl)-1,3,
5-triazine (15):18
3,4-Dichloro-2,2,3,4,4-pentafluorobutaneni-
trile (288 g) and 2-ethylhexylamine (8.2 g) were placed in a 500
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structure). GC purity 99.1%. Mp. 108 C.
mL flask. The mixture was heated at 90–150 C for 7 days. The
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Perfluoroanthracene (8):13 9,10-Dichloroanthracene (20 g),
KF (9.8 g), sulfolane (100 mL), and toluene (200 mL) were placed
product was distilled at 3 mmHg at 100–102 C, washed twice
with water, and dried. After distillation again in 3 mmHg vacuum,
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0
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in a 1 L flask. The mixture was heated at 118 C for 2 h. Toluene
was removed from the top of the flask and the flask was heated at
2
2,4,6-tris(2 ,3 -dichloro-1 ,1 ,2 ,3 ,3 -pentafluoropropyl)-1,3,5-tri-
azine was obtained as a colorless liquid in 48% yield. The material
was identified by GC mass spectrometry (a parent ion peak at
m=z ¼ 681 with a cracking pattern consistent with the objective
structure). GC purity 99.3%.
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10 C for 4 h. Water was added in the flask, the obtained solid
was filtered, and then washed twice with water, and dried. The sol-
id was recrystallized from chloroform. The perfluoroanthracene
was obtained as a pale yellow powder in 56% yield. Mp. 208
0
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0
2,4-Bis(2 ,3 -dichloro-1 ,1 ,2 ,3 ,3 -pentafluoropropyl)-6-pen-
tafluorophenyl-1,3,5-triazine (16):18
3,4-Dichloro-2,2,3,4,4-
pentafluorobutanenitrile (45 g) and NH3 were placed in a 100
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C. The material was identified by GC mass spectrometry (a pa-
rent ion peak at m=z ¼ 358 with a cracking pattern consistent with
the objective structure). GC purity 99.0%.
Perfluoro-1,3,5-triphenylbenzene (9):14 Bromopentafluoro-
benzene (148 g) and tetrahydrofuran (500 mL) were placed in a
mL stainless steel autoclave. The contents of the reactor were stir-
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red at 30 C for 5 days. After the NH3 was purged, the product
was placed in another 200 mL flask. 3,4-Dichloro-2,2,3,4,4-penta-
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2
solution (600 mL) was added to the flask at 5 C for 2 h. CuI
(
ture below 10 C. 1,4-Dioxane (200 mL) was added to the flask
and the mixture was stirred for 30 min. 1,3,5-Trifluorotriiodoben-
zene was quickly added to the flask. The flask was heated at 70 C
for 20 h. The mixture was poured into water and the precipitated
solid was extracted by hot hexane and recrystallized twice from
hexane. Perfluoro-1,3,5-triphenylbenzene was obtained as a white
crystal in 43% yield. The material was identified by GC mass
spectrometry (a parent ion peak at m=z ¼ 630 with a cracking pat-
tern consistent with the objective structure). GC purity 99.9%.
L flask. 1 mol/L ethylmagnesium bromide in tetrahydrofuran
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fluorobutanenitrile (40 g) was slowly added in the flask at 50 C
for 1 h, and pentafluorobenzoyl chloride (46 g) was slowly added.
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172 g) was added in the mixture while maintaining the tempera-
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After heating at 50 C for 4 h, the product was poured into water
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and dried. The liquid was distilled at 3 mmHg and 128–130 C,
0
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2,4-bis(2 ,3 -dichloro-1 ,1 ,2 ,3 ,3 -pentafluoropropyl)-6-pentafluo-
rophenyl-1,3,5-triazine was obtained in 62% yield. The material
was identified by GC mass spectrometry (a parent ion peak at
m=z ¼ 647 with a cracking pattern consistent with the objective
structure). GC purity 99.2%.
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The test methods described below were used in this study.
Blending Test, Mixing the Perfluorinated Polymer and the
Dopants. The miscibility of the dopants in the perfluorinated
polymer and Tg at the composition corresponding to the fiber core
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Mp. 152 C.