Synthesis of aliphatic diamine and polyetherimide with long perfluoroalkyl side chain

Article abstract of DOI:10.1016/S0022-1139(02)00164-1

The monomer, 2-(perfluorohexylmethyl)butan-1,4-diamine (TFD), was prepared from itaconic acid dimethyl ester via the addition of perfluorohexyl iodide followed by the gradual transformation of ester groups into amino groups. The polymerization of bisphenol-A diphthalic anhydride (BAPA) with TFD led to hydrophobic fluorinated polyetherimide (FPEI) with R_F=C₆F₁₃ side chain. This polymer makes it possible to cast films.

Full text of DOI:10.1016/S0022-1139(02)00164-1

Journal of Fluorine Chemistry 117 (2002) 27±33
Synthesis of aliphatic diamine and polyetherimide
with long per¯uoroalkyl side chain
*
Ricardo Escarcena Romero, Andre Mas , Philippe Laurent,
Â
FrancËois Schue, Hubert Blancou
Â
Organisation Moleculaire Evolution et Materiaux Fluores, UMR 5073 CNRS, Universite Montpellier II,
Á
Place Eugene Bataillon, 34095 Montpellier Cedex 5, France
Â
Â
Â
Â
Received 15 March 2002; received in revised form 1 July 2002; accepted 6 July 2002
Abstract
The monomer, 2-(per¯uorohexylmethyl)butan-1,4-diamine (TFD), was prepared from itaconic acid dimethyl ester via the addition of
per¯uorohexyl iodide followed by the gradual transformation of ester groups into amino groups. The polymerization of bisphenol-A
diphthalic anhydride (BAPA) with TFD led to hydrophobic ¯uorinated polyetherimide (FPEI) with RF ˆ C6F13 side chain. This polymer
makes it possible to cast ®lms.
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Fluorinated-alkylmethyldiamines; Fluorinated polyetherimide; Hydrophobic non-porous ®lms
1. Introduction
¯uorinated diamines are available and often they do not
show suf®cient structural qualities to enhance the ¯exibility.
It seems proved that a strong hydrophobicity of polymers is
generally connected to the presence of long ¯uorinated alkyl
chains±(CF2)n±CF3 ®xedonthemainchain[9±12].Moreover,
according to the n value, these pendant chains can gradually
change the interchain distances, the solid morphology and the
bulk structure, ®nally bringing about important consequences
for the rigidity±¯exibility characteristics of the materials.
All things considered, hydrophobicity and easy processing,
we performed the synthesis of a new series of polyetherimides
and copolyetherimides containing pendant per¯uoroalkyl
chains by polymerizing BAPA with a mixture of m-phenyle-
nediamine (m-PDA) and 2,3-bis(2,2,3,3,4,4,5,5,5-nona¯uor-
opentyl)butan-1,4-diamine (NFD) [13]. This series is now
extended using 2-(2,2,3,3,4,4,5,5,6,6,7,7,7-trideca¯uorohep-
tyl)butan-1,4-diamine; 2-(per¯uorohexylmethyl)butan-1,4-
diamine (TFD). This article describes the synthesis and
characterization of TFD and the related polyetherimide based
on the polymerization of BAPA with TFD.
Fluoropolymers [1] and particularly ¯uorinated polyi-
mides [2,3] are the subject of an intensive development
with regard to their interesting thermal, chemical and phy-
sical properties. The hydrophobic nature of the ¯uorinated
polyimides makes them potentially attractive for coating
applications, casing and sheathing as well as speci®c tech-
nologies. Recently, they were selected for preparing selec-
tive dense membranes used in organic±organic liquid
mixtures separation [4]. However, the transformation pro-
cessing of these thermoplastic materials and the mechanical
properties of the ®lm products are often sensitive points due
to the rigidity of the macromolecules chains. Indeed, more
often than not the aromatic groups that are involved in the
polymer structure may lead to brittleness.
The most common ¯uorinated polyimides are obtained
via the polymerization of 2,20-bis[3,4-(dicarboxyphenyl)-
hexa¯uoropropan]dianhydride (6FDA) with ¯uorinated or
non-¯uorinated aromatic diamines [5±8] giving materials
showing a variable fragility. Bisphenol-A diphthalic anhy-
dride (BAPA), with or without ¯uoromethyl groups, brings
to some extent ¯exibility properties to the polymer chain
thanks to the ether linkage. On the other hand, very few
* Corresponding author. Tel.: ‡33-4-6714-3858; fax: ‡33-4-6763-1046.
E-mail address: mas@univ-montp2.fr (A. Mas).
0022-1139/02/$ ± see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 1 1 3 9 ( 0 2 ) 0 0 1 6 4 - 1

28
R.E. Romero et al. / Journal of Fluorine Chemistry 117 (2002) 27±33
2. Results and discussions
5 or 8, were unsuccessful. Particularly, we tried the puri®ca-
tion by salt formation as well as by column chromatography.
We noticed the instability of the molecule and its partial
degradation in such experimental conditions. In fact, dia-
mines of this kind are very sensitive to the carbonation and
require to be protected from air. An alternative solution
was the puri®cation of the diphthalate 5 by column chro-
matography using silica and a 25% ethyl acetate/75%
petroleum ether mixture as eluant. The deprotection of 5,
leading to 1, was carried out just before the polymerization.
The NMR spectra were consistent with the TFD structure
and showed no impurity above 3% concentration. Currently,
we are attempting to elaborate a speci®c puri®cation method
of 1.
2.1. Synthesis of 2-(perfluorohexylmethyl)butan-1,
4-diamine
The synthesis of the per¯uorinated diamine began by
introducing the per¯uorinated side chain. The starting mole-
cule was itaconic acid dimethyl ester which can react
ef®ciently with various per¯uorinated alkyl iodides (RFI
with RF ˆ C4F9, C6F13) [14]; then the two diesters groups
were transformed into amine groups in good yield using
classic reactions.
The synthesis of the diamine was carried out as outlined in
Scheme 1. The reaction between per¯uorohexyl iodide and
itaconic acid dimethyl ester in presence of active zinc led to
¯uorinated diester 2 which was reduced to the corresponding
diol 3 using LiAlH4 and THFas a solvent. The transforma-
tion of the diol into the corresponding dihalide (4 or 7) was
done using various procedures (HBr/H2SO4, PBr3, I2/
H3PO4±P2O5). The best results were obtained by substitu-
tion of the tosylated derivative (6) with NaI; diiodide 7 was
obtained in more than 80% yield.
Starting with the dihalide (4 or 7), the diamine was formed
following the classic method of Gabriel. The treatment of
the bromide derivative 4 with potassium phthalimide in
DMFat 80 8C provided the corresponding diphthalate 5
in a good yield (65%). The deprotection of 5 with hydrazine
gave the crude diamine 1 (TFD) in satisfactory yield (59%).
Another method was to treat the diiodide derivative 7 with
sodium azide. This gave the corresponding azide 8 which
was reduced to the desired diamine 1 with H2/Pd±C in a
good yield (89%). Many attempts to purify 1, obtained from
2.2. Synthesis of fluorinated polyetherimide (FPEI)
Fluorinated polyetherimide (FPEI) was prepared by heat-
ing an equimolar amount of BAPA and fresh TFD in N-
methyl-pyrrolidinone (NMP) under argon atmosphere at
120 8C for 48 h (Scheme 2).
Generally, non-¯uorinated diamines react with dianhy-
drides at room temperature. In the case of ¯uorinated
diamines, we observed a slow increase of the solution
viscosity with time and we deduced a lower reactivity of
the ¯uorinated diamine than those of the non-¯uorinated
diamines. This most probably results from its strong elec-
tron-withdrawing nature. Therefore, to convert the full
amount of TFD, 120 8C temperature and long reaction time
conditions were indispensable. An incomplete imidization
of the polymer was ®rst obtained. In this kind of step-
reaction, generally a poly(ether amic acid) intermediate
Scheme 1.

R.E. Romero et al. / Journal of Fluorine Chemistry 117 (2002) 27±33
29
Scheme 2.
was obtained by the opening of the anhydride ring of BAPA
[15]. Then, one carboxylic acid group and one amide group
result from the reaction of BAPA with the diamine. So, the
poly(ether amic acid) intermediate and the expected poly-
etherimide were present together in the solution. The mix-
ture of the polymers was precipitated in a EtOH/H2O
mixture. To achieve chain extension to higher molecular
weights and to complete imidization, the mixture of poly-
mers was dried in a vacuum oven at 140 8C for 12 h,
allowing the dehydration of the amid-acid structure to lead
to the imide structure and to give FPEI as the only product.
In order to evaluate the characteristics of FPEI we also
polymerized BAPAwith m-PDA. The resulting polymer, that
we named UPEI, was obtained by a similar procedure. It
provided us with a useful comparison. In fact, UPEI is the
normal ULTEM 1000 polyether imide developed by General
Electric Plastics.
According to the gel permeation chromatography (GPC)
data, molecular weights Mn and Mw are not very high but
the polydispersity value seems to be correct (Table 1). The
purity degree of TFD can account for the relatively low
molecular weight. Differential scanning calorimetry (DSC)
showed that FPEI is amorphous. The glass transition tem-
perature, Tg, decreases from 217 8C for the UPEI sample
to 113 8C for FPEI. This can be attributed to the aliphatic
chain segments leading to an easy change in the conforma-
tion of the macromolecules. Furthermore, the bulky ¯uori-
nated side chains keep the macromolecules away from
each other and may allow a few movements of all chain
segments.
UPEI and ULTEM showed slightly different degradation
temperatures, respectively 385 and 430 8C (literature data)
under atmosphere of argon, partly because the polymer
samples were not prepared in the same manner. UPEI

30
R.E. Romero et al. / Journal of Fluorine Chemistry 117 (2002) 27±33
Table 1
The method developed by Owens and Wendt [16] allows
the calculation of the surface energy gs, its dispersive (gds ) and
Characteristics of polyetherimides
polar (gps ) components, from the contact angle values (y), the
Mw
Mn
Tg (8C) Td (8C, air)a
Td (8C, argon)a
super®cial energy of two liquids (gL H O ˆ 78:8 m NmÀ1 and
2
10%
50%
10%
50%
gL CH I ˆ 50:8 mN mÀ1),thedispersivecomponent(gdL H O
ˆ
2
2
2
21:8 m NmÀ1 and gLd CH I ˆ 49:5 mN mÀ1) and polar com-
UPEI
FPEI
30,000 12,000 217
12,200 6,000 113
385
440
±
375
485
±
2
2
ponent (gpL H O ˆ 51 mN mÀ1 and gLp CH I ˆ 1:3 m NmÀ1).
545
525
2
2 2
a Atmosphere under which thermal degradation temperature, defined as
x% weight loss, was measured.
3.2. 2-(Perfluorohexylmethyl) succinic acid dimethyl
ester (2)
Table 2
Contact angles and surface energies of polyetherimide
To a stirred solution of itaconic acid dimethyl ester
(70.5 ml, 0.5 mol), propionic acid (37 ml, 0.5 mol) and
activated zinc (32.7 g, 0.5 mol) in CH2Cl2 (250 ml), per-
¯uorohexyliodide (108 ml, 0.5 mol) was added dropwise
during 1.5 h. The temperature of the mixture rose to
40 8C. The reaction mixture was dissolved in Et2O (2 l)
and the solution was successively washed with 10% aqueous
HCl (3 Â 200 ml), water (3 Â 200 ml) and dried over
Na2SO4. Removal of solvent gave crude per¯uorohexyl
derivated 2 (215.6 g, 90%), which was used for the next
step without further puri®cation.
IR (nmax, cmÀ1): 2959, 1740, 1440, 1351, 1145, 1034.
1H NMR (400 MHz, CDCl3): d (ppm): 3.53 (s, 3H, OMe),
3.49 (s, 3H, OMe), 3.02 (q, 1H, J ˆ 6 Hz, H-2), 2.60 (dd,
1H, J ˆ 17 and 7 Hz, H-3A), 2.51 (dd, 1H, J ˆ 17 and 6 Hz,
H-3B), 2.45 (m, 1H, H-10A), 2.20 (m, 1H, H-1B0 ).
yH O (8) yCH I (8) gds (mN mÀ1
)
gps (mN mÀ1
)
gs (mN mÀ1
)
2
2 2
UPEI 88
FPEI 90
32
77
44.5
15.8
0.8
7.0
45.3
22.8
samples result from the cast-evaporation method and
ULTEM samples result from extrusion.
The degradation temperature is affected by the ¯uorinated
side chains. A loss of 10% weight of polymer occurred
above 440 8C under air and 485 8C under argon indicating
reasonable stability of the polymers (Table 1).
The wettability, measured by the water contact angle,
slightly decreases from UPEI to FPEI. The combination of
water and diiodomethane contact angles shows the increase
of hydrophobicity (gs ˆ 22:8 mN mÀ1) of the FPEI ®lm
surface (Table 2).
We tried to elaborate ®lms from a 10% weight polymer
solution in NMP which was cast on a glass plate and then the
solvent evaporated. The ®rst attempts gave ®lms greater than
30 mm thick standing the test of handling.
13C NMR (100 MHz, CDCl3): d (ppm): 173.4 (C-1),
171.6 (C-4), 52.9, 52.4 (2OMe), 35.8 (C-3), 34.7 (C-2),
31.9 (C-10) and 118.7 (m, CF3), 116.1, 113.7, 113.2, 111.4,
108.9 (5m, 5CF2).
19FNMR (235 MHz, CDCl 3): d (ppm): À81.9 (CF3),
À114.3, À122.8, À123.9, À124.5, À127.2 (5CF2).
‡
FABMS: m/z (%): 479 (M ‡ H) (28), 447 (100), 403
(23), 433 (14), 389 (19), 377 (26), 209 (5), 169 (17), 117
(12), 55 (100), 31 (86).
3. Experimental
3.1. General
3.3. 2-(Perfluorohexylmethyl)butan-1,4-diol (3)
1H, 13C, 19FNMR spectra were recorded with a Bruker
AC instrument. Tetramethyl silane (TMS) and ¯uorotri-
chloromethane were used as internal references for 1H
and 19FNMR spectra, respectively. TFIR spectra were
recorded with a Bruker IFS 25 spectrophotometer. Mole-
cular weights of polymers were determined by GPC with a
Waters instrument using tetrahydrofuran (THF) as eluant.
The system was calibrated with polystyrene standards. DSC
data were obtained using a Mettler DSC 30 instrument under
N2 atmosphere. Thermogravimetric analysis (TGA) was
effected using a Netzch Garatebau STA 409 instrument
under atmosphere of air or argon.
LiAlH4 (9.25 g, 0.24 mol) was added to a solution of 2
(105.8 g, 0.22 mol) in dry THF(2 l) at 0 8C. The reaction
mixture was stirred for 2 h at room temperature. After that,
few drops of water were added at 0 8C until the excess
LiAlH4 was eliminated. Then, ether (2 l) and a mixture of
Na2SO4/NaHCO3 (1:1, 200 g) were added and the mixture
was stirred for 2 h. After ®ltration and evaporation of the
solvent, compound 3 (84.5 g, 91%) was obtained as a pale
viscous liquid.
IR (nmax, cmÀ1): 3330, 2944, 1237, 1145, 1047, 695.
1H NMR (400 MHz, CDCl3): d (ppm): 3.7±3.5 (m, 4H, H-
1,4), 2.2±1.7 (m, 5H, H-2,3,10).
Static measurements of the contact angle were made with
a Kruss G1 apparatus. The polymer solution was placed on a
metal support and when the solvent evaporated, a thin ®lm
was formed and the measurements were made with water
and diiodomethane.
13C NMR (100 MHz, CDCl3): d (ppm): 65.4 (C-1), 60.3
(C-4), 35.7 (C-3), 32.6 (C-2), 31.9 (C-10) and 121.8 (m,
CF3), 119.3, 116.1, 113.3, 111.2, 108.2 (5 m, 5CF2).
19FNMR (235 MHz, CDCl 3): d (ppm): À81.5 (CF3),
À113.7, À122.5, À123.6, À124.2, À126.9 (5CF2).

R.E. Romero et al. / Journal of Fluorine Chemistry 117 (2002) 27±33
31
‡
FABMS: m/z (%): 423 (M ‡ H) (28), 405 (100), 403
stirred at 0±5 8C for 12 h, then ice (100 g) was added and the
stirring continued for 30 min. The solution was extracted
with Et2O (3 Â 1 l) and the combined organic layers were
successively washed with water (3 Â 200 ml), 10% aqueous
HCl (3 Â 200 ml), 5% aqueous NaHCO3 (3 Â 200 ml),
brine (3 Â 200 ml) and dried over Na2SO4. Removal of
the solvent gave crude tosyl derivate 6 as pale yellow oil.
IR (nmax, cmÀ1): 2972, 2950, 1599, 1440, 1401, 1366, 665.
1H NMR (250 MHz, CDCl3): d (ppm): 7.71 (d, 4H,
J ˆ 8 Hz, Ar), 7.31 (d, 2H, J ˆ 8 Hz, Ar), 7.27 (d, 2H,
J ˆ 8 Hz, Ar), 3.95 (m, 4H, H-1,4), 2.40 (s, 6H, ArCH3),
2.24 (m, 1H, H-2), 2.2±1.9 (m, 2H, H-10), 1.78 (m, 2H,
J ˆ 6 Hz, H-3).
(23), 387 (22), 119 (14), 69 (95), 31 (85).
3.4. 1,4-Dibromo-2-(perfluorohexylmethyl) butane (4)
PBr3 (3 ml, 30 mmol) was added to diol 3 (10.1 g,
23.9 mmol) at 0 8C. After 30 min, the mixture was heated
at 80 8C for 12 h. After that, 10 ml of water was added at 0 8C
and two layers appeared. The aqueous layer was extracted
with Et2O (3 Â 100 ml). The Et2O solutions were added to
the organic layer. All the solutions were washed with 10%
aqueous Na2CO3 (3 Â 50 ml), followed by brine (3 Â 50 ml)
and dried over Na2SO4. The ®ltrate was concentrated to give
an oil which was puri®ed by distillation. The dibromo
derivated 4 (6.3 g, 48%) was obtained as a colorless oil.
IR (nmax, cmÀ1): 2972, 1230, 1150, 490.
13C NMR (100 MHz, CDCl3): d (ppm): 145.8, 145.6 (Cp,
Ar), 130.4 (4CH, m-Ar), 128.3 (4CH, o-Ar), 133.0, 132.6
(2C, Ar), 70.7 (C-1), 67.2 (C-4), 31.4 (C-10), 30.8 (C-3), 28.8
(C-2), 22.0 (2CH3Ar) and from 108 to 122 (6 m, weak
intensity, CF3±(CF2)5±).
1H NMR (400 MHz, CDCl3): d (ppm): 3.52 (m, 2H, H-1),
3.38 (m, 2H, H-4), 2.49 (s.a., 1H, H-2), 2.3 (m, 1H, H10A),
2.1±1.9 (m, 3H, H-3,10B).
19FNMR (235 MHz, CDCl ): d (ppm): À81.4 (CF3),
3
13C NMR (100 MHz, CDCl3): d (ppm): 37.5 (C-1), 35.9
(C-3), 33.5 (C-10), 31.3 (C-2), 39.9 (C-4) and 121.3 (m,
CF3), 118.8, 116.3, 113.8, 111.4, 108.6 (5m, 5CF2).
À113.7, À122.5, À123.6, À124.2, À126.8 (5CF2).
‡
FABMS:m/z(%):731(M ‡ H) (4),638(100),559(6),482
(7), 403 (11), 387 (11), 173 (35), 155 (98), 91 (100), 31 (52).
19FNMR (235 MHz, CDCl ): d (ppm): À81.5 (CF3),
3
À113.5, À122.5, À123.6, À124.2, À126.9 (5CF2).
3.7. 1,4-Diiodo 2-(perfluorohexylmethyl) butane (7)
‡
FABMS: m/z (%): 548 (M ‡ H) (8), 467 (38), 387 (55),
367 (9), 327 (10), 113 (18), 109 (34), 69 (100), 41(82).
Solid NaI (26.3 g, 175.2 mmol) was added to a stirred
solution of 6 (32 g, 43.8 mmol) in acetone (300 ml) and the
mixture was heated under re¯ux for 3 h. Then, the solvent
was evaporated and the residue diluted with water (300 ml).
The aqueous phase was extracted with Et2O (3 Â 500 ml)
and the combined organic layers were washed with H2O
(3 Â 150 ml), 10% aqueous solution of Na2SO3
(3 Â 150 ml), 5% aqueous NaHCO3 (3 Â 150 ml), brine
(3 Â 150 ml) and dried over Na2SO4. The ®ltrate was con-
centrated to give an oil which was puri®ed by column
chromatography with petroleum ether±Et2O (98/2) as eluant
affording iodo derivate 7 (23 g, 82%) as a colorless oil.
IR (nmax, cmÀ1): 2950, 1263, 1234, 1182, 1145, 714.
1H NMR (400 MHz, CDCl3): d (ppm): 3.32 (d, 1H,
J ˆ 11 Hz, H-1A), 3.27 (dd, 1H, J ˆ 11 and 3 Hz, H-1B),
3.16 (dd, 1H, J ˆ 11 and 6 Hz, H-4A), 3,04 (dd, 1H,
J ˆ 10:6 Hz, H-4B), 2.30 (m, 1H, H-2), 2,00±1,80 (m,
4H, H-3,10).
3.5. 1,4-(Di-N-phthalimide)-2-(perfluorohexylmethyl)
butane (5)
Solid potassium diphthalimide (0.928 g, 4.86 mmol) was
added to a stirred solution of 4 (1.065 g, 1.94 mmol) in DMF
(5 ml) and the mixture was heated at 80 8C for 4 h. Then,
water was added (5 ml) and the formed precipitate was
®ltrated off, dissolved in CH2Cl2 and the solution was washed
many times with water and dried over Na2SO4. The ®ltrate
was concentrated to give 5 (0.822 g, 62%) as a white solid.
IR(nmax, cmÀ1):3027, 2950, 2870, 1780, 1720, 1623, 1487.
1H NMR (400 MHz, CDCl3): d (ppm): 7.85 (m, 4H, Ar),
7.74 (m, 4H, Ar), 3.84 (m, 4H, H-1,4), 2.48 (q, 1H,
J ˆ 6 Hz, H-2), 2.40±2.26 (m, 2H, H10), 1.88 (c, 2H,
J ˆ 6 Hz, H-3).
13C NMR (100 MHz, CDCl3): d (ppm): 168.6, 167.0
(4CO), 134.6, 134.4 (4CH, m-Ar), 132.4, 132.2 (4C, Ar),
123.9, 123.6 (4CH, o-Ar), 42.1 (C-1), 35.6 (C-4), 33.2 (C-
10), 31.5 (C-3), 29.9 (C-2) and 121.4 (m, CF3), 119.1, 116.2,
113.3, 115.5, 108.8 (5m, 5CF2).
13C NMR (100 MHz, CDCl3): d (ppm): 38.8 (C-3), 35.1
(C-10), 32.7 (C-2), 13.6 (C-1), 2.0 (C-5) and 121.3 (m, CF3),
118.9, 116.1, 113.8, 113.2, 111.4 (5m, 5CF2).
19FNMR (235 MHz, CDCl ): d (ppm): À81.9 (CF3),
3
19FNMR (235 MHz, CDCl ): d (ppm): À81.4 (CF3),
À113.4, À122.7, À123.8, À124.4, À127.2 (5CF2).
3
‡
À113.2, À122.4, À123.5, À124.0, À126.8 (5CF2).
FABMS: m/z (%): 642 (M ‡ H) (8), 641 (7), 515 (91),
‡
FABMS: m/z (%): 681 (M ‡ H) (25), 551 (6), 534 (9),
387 (4), 327 (8), 155 (35), 119 (28), 69 (100), 31 (92).
404 (11), 160 (100), 105 (40), 31 (58).
3.8. 2-(Perfluorohexylmethyl) butane 1,4-diazide (8)
3.6. 2-(Perfluorohexylmethyl)butan-1,4-diol ditosylate (6)
Solid NaN3 (5 g, 77.1 mmol) was added to a stirred
solution of 4 (12.4 g, 19.3 mmol) in DMF(50 ml) and the
mixture was heated at 80 8C for 4 h. Then, water was added
To a solution of 3 (84.5 g, 0.20 mol) in pyridine (500 ml)
at 0 8C was added TsCl (99.1 g, 0.52 mol). The mixture was

32
R.E. Romero et al. / Journal of Fluorine Chemistry 117 (2002) 27±33
‡
(100 ml) and the mixture was extracted with Et2O
(3 Â 500 ml). The combined organic layers were washed
with brine (3 Â 100 ml) and dried over Na2SO4. The ®ltrate
was concentrated to give an oil which was puri®ed by column
chromatography with petroleum ether±Et2O (95/5) as eluent
giving diazide derivate 8 (8.8 g, 96%) as a colorless oil.
IR (nmax, cmÀ1): 2950, 2084, 1366, 1236, 1147, 812, 732.
1H NMR (400 MHz, CDCl3): d (ppm): 3.42 (dd, 1H,
J ˆ 13 and 5 Hz, H-1A), 3.39 (dd, 1H, J ˆ 13 and 4 Hz, H-
1B), 3.31 (t, 2H, J ˆ 7 Hz, H-4), 3.04 (dd, 1H, J ˆ 10:6 Hz,
H-4B), 2.30 (m, 1H, H-2), 2.00±1.80 (m, 4H, H-3, 10).
13C NMR (100 MHz, CDCl3): d (ppm): 53.1 (C-1), 47.7
(C-4), 31.1 (C-10), 30.4 (C-3), 28.7 (C-2) and 121.5 (m,
CF3), 118.9, 116.1, 113.8, 111.2, 108.8 (5m, 5CF2).
19FNMR (235 MHz, CDCl 3): d (ppm): À82.0 (CF3),
À113.7, À122.7, À123.8, À124.5, À127.3 (5CF2).
FABMS: m/z (%): 421 (M ‡ H) (100), 404 (98), 402
(92), 388 (10), 384 (9), 136 (12), 169 (100), 31(100).
3.10. Fluoropolyetherimide FPEI
Solid BAPA (2.134 g, 4.1 mmol) was added to a stirred
solution of 1 (1.801 g, 4.1 mmol) in NMP (N-methyl-pyr-
rolidone, 33 ml) under atmosphere of argon. The mixture
was heated at 120 8C for 2 days. Then, it was poured into
aqueous ethanol (200 ml H2O and 100 ml EtOH) and the
formed precipitate was ®ltrated off and dried under vacuum
at 140 8C for 12 h. A brown dark solid of FPEI was obtained
(3.52 g, 90%).
IR (nmax, cmÀ1): 2959, 1740, 1440, 1351, 1145, 1034.
1H NMR (400 MHz, CDCl3): d (ppm): 7.67 (m, 2H, H-7,
H-32), 7.22 (m, 6H, H-9, H-12, H-16, H-22, H-24, H-28),
7.18 (m, 2H, H-6, H-31), 6.42 (m, 4H, H-13, H-15, H-22, H-
24), 3.66 (m, 4H, H-36, H-39), 2.33 (m, 1H, H-37), 2.30±
2.05 (m, 2H, H-10), 1.72 (m, 2H, H-38), 1.65 (s, 6H, H-18, H-
19).
‡
FABMS: m/z (%): 642 (M ‡ H) (8), 641 (7), 515 (91),
387 (4), 327 (8), 155 (35), 119 (28), 69 (100), 31 (92).
3.9. 2-(Perfluorohexylmethyl)butan-1,4-diamine (1)
13C NMR (100 MHz, CDCl3): d (ppm): 168.5, 168.1 (C-1,
C-3, C-33, C-35); 164.1, 163.9 (C-8, C-27); 153.2, 153.1 (C-
11, C-23); 148.0, 147.9 (C-14, C-20); 134.3 (C-4, C-29);
129.1 (C-13, C-15, C-21, C-25); 125.8, 125.6 (C-6, C-31);
125.5, 125.3 (C-5, C-30); 123.0, 122.8 (C-7, C-32); 120.4
(C-12, C-16, C-22, C-24); 43.0 (C-17); 42.1 (C-36), 35.1 (C-
39), 33.1 (C-10); 31.6 (C-38); 31.4 (C-18, C-19); 28.1 (C-37)
and 120.3 (m, CF3), 119.5, 116.1, 114.0, 112.4, 109.0 (5m,
5CF2).
Method A: H2 was added at room temperature and under
atmospheric pressure to a vigorously stirred suspension of
10% Pd/C catalyst (50 mg) and 1.31 g (2.8 mmol) of 8 in
MeOH (15 ml). After 4 h, the reaction was completed. The
mixture was ®ltered through celite and concentrated to give
diamine 1 (1.05 g, 89%) as a white pale oil.
Method B: To a solution of 5 (0.800 g, 1.17 mmol) in
EtOH (5 ml), hydrazine (1 ml) was added and the mixture
was stirred and heated with re¯ux until a white solid
appeared. Then, it was cooled to 0 8C, acidi®ed (pH 1) with
19FNMR (235 MHz, CDCl 3): d (ppm): À81.4 (CF3),
À113.1, À122.4, À123.5, À124.0, À126.8 (5CF2).
aqueous hydrochloric acid and re¯uxed again for 30 min.
After this time, the precipitate of N,N-phthaloylhydrazine
was ®ltrated off and washed with water. The water solution
was alkalined with aqueous NaOH, extracted with ether and
dried over Na2SO4. The ®ltrate was concentrated to give
crude diamine 1 (0.290 g, 59%) as pale white oil.
IR (nmax, cmÀ1): 3372, 3300, 2936, 1587, 1147, 1365,
1238, 812.
Acknowledgements
We gratefully acknowledge the ®nancial support obtained
from the European Commission, TMR Research Networks,
Fluorine as a unique tool for engineering molecular proper-
ties, contract number ERBFMRXCT 970120 and the ATO-
FINA company for supplying the starting per¯uorinated
molecules.
1H NMR (400 MHz, CD3OD): d (ppm): 2.6 (m, 4H, H-
1,4), 2.22 (m, 1H, H10A), 1.99 (m, 1H, H10B), 1.90 (spt., 1H,
J ˆ 6 Hz, H-2), 1.55 (m, 2H, H-3).
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CF3), 118.6, 116.0, 113.3, 111.2, 108.7 (5m, 5CF2).
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