Hybrid organic-inorganic gels containing perfluoro-alkyl moieties

Article abstract of DOI:10.1016/S0022-1139(00)00211-6

Perfluoroalkyltrialkoxysilanes were prepared by hydrosilylation of the allylic or vinylic derivatives with trialkoxysilane or with trichlorosilane (followed by a quantitative methanolysis). The hydrolysis and polycondensation of these precursors were performed in the presence of tetrabutylammoniumfluoride (TBAF) as the catalyst, leading to a series of new polysilsesquioxanes, which were characterized by solid state ¹³C and ²⁹Si CPMAS NMR. The porosity and surface area of these materials were determined by N₂ absorption experiments. Thermogravimetric analyses (TGA) were also performed. The surface properties of films prepared from these silsesquioxanes were studied by contact angle measurements. The hybrids having fluoroalkyl groups at the surface of the material showed a better thermostability and a higher hydrophobic and oleophobic character than their hydrocarbon analogues.

Full text of DOI:10.1016/S0022-1139(00)00211-6

Journal of Fluorine Chemistry 104 (2000) 185±194
Hybrid organic±inorganic gels containing
per¯uoro-alkyl moieties
*
Bruno Ameduri, Bernard Boutevin, Joel J.E. Moreau ,
È
Hicham Moutaabbid, Michel Wong Chi Man
   Â
Laboratoire de Chimie Organometallique, UMR 5076, Heterochimie Moleculaire et Macromoleculaire,
Â
ENSC Montpellier, 8, rue de l'Ecole Normale, 34296 Montpellier, Cedex 5, France
Received 25 October 1999; accepted 21 December 1999
Abstract
Per¯uoroalkyltrialkoxysilanes were prepared by hydrosilylation of the allylic or vinylic derivatives with trialkoxysilane or with
trichlorosilane (followed by a quantitative methanolysis). The hydrolysis and polycondensation of these precursors were performed in the
presence of tetrabutylammonium¯uoride (TBAF) as the catalyst, leading to a series of new polysilsesquioxanes, which were characterized
by solid state 13C and 29Si CPMAS NMR. The porosity and surface area of these materials were determined by N2 absorption experiments.
Thermogravimetric analyses (TGA) were also performed. The surface properties of ®lms prepared from these silsesquioxanes were studied
by contact angle measurements. The hybrids having ¯uoroalkyl groups at the surface of the material showed a better thermostability and a
higher hydrophobic and oleophobic character than their hydrocarbon analogues. # 2000 Elsevier Science S.A. All rights reserved.
Keywords: Sol±gel; Per¯uoroalkyl silsesquioxanes; Hybrid organic±inorganics; Silica based materials
1. Introduction
of ¯uorinated polysilsesquioxanes. Related materials pos-
sessing per¯uoroalkyl alkyl silyl groups are of interest as
novel UV and hydrophobic resistant coatings [15,37±39].
Water-repellent properties can be easily obtained upon sur-
face treatment of solid materials [39]. However, the hydro-
lysis and polycondensation of organotrialkoxysilanes can
provide an easy preparation of materials with covalently
retained ¯uorinated moieties, owing to the presence of a
non-hydrolysable C±Si bond.
In this paper, the syntheses of ¯uoroalkylmono- and bis-
trialkoxysilanes are described. These precursors led to new
hybrid silica gels, containing ¯uoroalkyl chains the proper-
ties of which were investigated and compared to those of
related materials containing analogous hydrocarbon chains.
Fluorinated polymers offer unique high-performance
properties rendering them particularly attractive for surface
modi®cation and protection [1±3]. In this ®eld many inves-
tigations have been developed for the protection of stone [4],
optical ®bers [5], leather [6], metals [7], paper [8], for the
waterproo®ng of textiles [9,10] or the protection of electro-
nic devices [11], and also for antifouling properties of paints
for boats [12,51]. The synthesis of ¯uorinated polymers
containing silicon atoms has already attracted the interest of
several authors. Particularly, ¯uorosilicones are valuable
materials since they combine excellent solvent resistance
[13], good thermal stability [14] [15] and low surface energy
[16±18]. The synthesis of ¯uorosilicones can be achieved
either by adding the ¯uorocarbon side-chain moieties to a
preformed siloxane [19,20] or by the polymerization of
suitable monomers [14,21±25].
2. Results and discussion
The synthesis of hybrid gels was performed by the
hydrolysis/condensation of trialkoxysilanes containing per-
¯uoroalkyl or alkyl chains.
Hybrid organic±inorganics constitute a unique class of
materials which can combine the properties associated to the
two components [26±30]. Our current interest in hybrid
silsesquioxanes [31±36], which are solids consisting of a
well de®ned hybrid network, led us to study the preparation
2.1. Synthesis of the silylated precursors
Two types of trialkoxysilanes were prepared: mono-sily-
lated (Scheme 1) and bis-silylated compounds (Schemes 2
and 3).
* Corresponding author. Fax: ‡33-4-6714-4353.
0022-1139/00/$ ± see front matter # 2000 Elsevier Science S.A. All rights reserved.
PII: S 0 0 2 2 - 1 1 3 9 ( 0 0 ) 0 0 2 1 1 - 6

186
B. Ameduri et al. / Journal of Fluorine Chemistry 104 (2000) 185±194
Scheme 1. Synthesis of pendant group monomers.
Scheme 2. Synthesis of spacer group containing monomers.
The mono-silylated precursors (II) were obtained in a
1,10-Bis(trimethoxysilyl)decane (IIIH) was prepared
from 1,10-dichlorodecane by reacting an in situ formed
Grignard reagent with chlorotrimethoxysilane in THF as
solvent.
The ¯uorocarbon analogue (IIIF) was prepared by hydro-
silylation of the corresponding a,o-diene with HSi(OEt)3
using a platinum catalyst in the absence of solvent [25,40].
In this case, ethoxy substituents at silicon were preferred to
methoxy groups. Owing to the higher thermal stability of the
former it allows an easy puri®cation of the silylated product
by distillation. Attempts to distil the monomer bearing
methoxy groups at silicon led to decomposition.
The synthesis of the precursors IVF and IVH with pendant
groups (Scheme 3) required the preparation of a triethox-
ysilylmethyl Grignard reagent [41] which reacted with
dichloromethylsilane to give the corresponding hydrogeno-
silane. Hydrosilylation with the unsaturated derivatives:
two-step reaction: hydrosilylation of the corresponding
vinylic or allylic alkyl and ¯uoroalkyl derivatives with
HSiCl3, in the presence of hexachloroplatinic acid, followed
by methanolysis (Scheme 1).
The ¯uorinated monomers were obtained quantitatively
by performing the hydrosilylation in a stainless steel auto-
clave or in sealed Carius tubes. The hydrosilylation of the
hydrocarbon monomers was successfully achieved in sealed
tubes. The methanolysis step was quantitative and was
performed either with or without triethylamine (NEt3).
Two kinds of bis trialkoxysilyl monomers were consid-
ered: the alkyl or per¯uorinated group being located either
in the chain as a spacer group between the two silicon atoms
or in a side-chain as a pendant group.
The monomers with a spacer group were obtained accord-
ing to two different methods as illustrated in Scheme 2.
Scheme 3. Synthesis of monofunctional silanes.

B. Ameduri et al. / Journal of Fluorine Chemistry 104 (2000) 185±194
187
The ®rst set of resonances at 49, 57 and 64 ppm
corresponds to the T (:CO3Si) units originating from the
hydrolysis of the organotrialkoxysilanes. A second set of
signals at 94, 102 and 110 ppm is attributed to the Q
(:SiO4) units produced by the hydrolysis of Si(OMe)4
(TMOS). It seems that gel G-IIF1 presents a higher degree
of condensation than gel G-IIH1. Although, the 29Si NMR
spectra were recorded using cross-polarisation techniques
[43], since the silicon atoms in gels G-IIH1 and G-IIF1 have
identical environments, the observed intensities of the sig-
nals are related to the ratios of the various T1, T2, T3
substructures. This was previously observed in the case
of related silsesquioxane materials [31,34]. The spectra in
the T sites region show in the case of gel G-IIH1 the
presence of T1 [: SiC(OSi)(OH)2] substructures, at
50.6 ppm, whereas this is not observed in the spectrum
of gel G-IIF1. Additionally, the relative intensities of the
signals corresponding to T2 [: SiC(OSi)2(OH)] units at
58 ppm and T3 [: Si C(OSi)3] substructures at 65 ppm,
with higher intensity of the T3 signal in the case of gel G-
IIF1, are indicative of a higher degree of condensation
around silicon in gel G-IIF1.
Scheme 4. Synthesis of gels from monosilylated precursors.
undec-1-ene or allyl per¯uoro octane led to compounds IVH
and IVF, respectively.
2.2. Preparation and NMR characterisation of gels
2.2.1. Gels from monosilylated precursors
The monosilylated precursors IIH and HF and ®ve mole
equivalent of tetramethoxysilane, Si(OMe)4 were hydro-
lysed in the presence of TBAF as catalyst (Scheme 4).
In the case of the hydrocarbon precursors (IIH0 and IIH1),
only methanol was used as solvent. For the per¯uorinated
ones (IIF0 and IIF1), owing to their insolubility in usual
organic solvents,
a mixture of solvents (methanol/
C6F13C2H4OH Ð v/v: 1/5) was necessary for obtaining
homogeneous solutions before gelation. These cogels are
called G-IIH0, G-IIH1, respectively, for those derived from
the hydrocarbon precursors, and G-IIF0, G-IIF1 for those
prepared from the ¯uorinated precursors. These materials
were analysed and characterized by 13C and 29Si solid state
NMR spectroscopies and by nitrogen adsorption measure-
ments according to BET [42].
2.2.2. Gels prepared from bis-silylated precursors with a
spacer group
In this case, methanol was used as solvent for the
hydrolysis of the hydrogenated precursor (IIIH) whereas
the ¯uorinated compound (IIIF) was hydrolysed in THF
(Scheme 5).
The solid state 13C CP-MAS NMR spectra clearly shows
that the organic moieties are retained in the materials. In the
®rst case (gel G-IIH1), ®ve sharp and distinct peaks at 13.9,
22.9, 29.9, 32.4 ppm (corresponding to the hydrocarbon
chain) and at 50.5 ppm (residual methoxy groups at silicon)
are observed. For gel G-IIF1, the spectrum was more
complex owing to coupling between the carbon and the
¯uorine atoms. The signals centered at 10.6 and 29.7 ppm
are attributed to the two carbon atoms of the hydrocarbon
segment and the broad signal with low intensity, in the 110±
115 ppm range, corresponds to the carbon atoms in the
¯uorocarbon part. A peak at 50.3 ppm was assigned to non-
hydrolyzed residual methoxy groups at the silicon atoms.
The 29Si CP-MAS NMR spectra of G-IIH1 and of G-IIF1,
gels are shown in Fig. 1a and b, respectively.
Transparent gels formed rapidly, these were dried to
give the xerogels G-IIIH and G-IIIF, respectively. The
13C CP-MAS solid state NMR spectrum of the hydrocarbon
gel, G-IIIH showed four peaks (12.5, 23.0, 29.8 and
33.1 ppm) corresponding to the carbon atoms of the chain
and another peak at 49.8 ppm (residual methoxy groups
at silicon), in agreement with the molecular structure
of the precursor. In the case of gel G-IIIF, the signals
centered at 17.6 and 34.6 ppm were assigned to the
hydrocarbon part of the chain and the broad signal (100±
125 ppm) centered at 115 ppm was attributed to ¯uorinated
carbons.
Fig. 2a and b show the 29Si CP-MAS solid state NMR
spectra of G-IIIH and G-IIIF, respectively. Only resonances
corresponding to T (:CO3Si) substructures are present. The
absence of Q units in both spectra clearly demonstrates that
there is no C±Si bond cleavage occurring during the hydro-
lysis/condensation process.
Fig. 1. Solid state 29Si CP-MAS NMR of G-IIH1 (a) and G-IIF1 (b).
Scheme 5. Synthesis of gels bearing spacer group.

188
B. Ameduri et al. / Journal of Fluorine Chemistry 104 (2000) 185±194
Fig. 2. Solid state 29Si CP-MAS NMR of G-IIIH (a) and GIIIF (b).
Whereas the spectrum of G-IIIH exhibits three distinct
For G-IVF, an intense broad signal assigned to the carbon
atoms bonded to the central silicon atom is observed at
0.7 ppm. A broad signal at 36.5 accounts for the hydro-
carbon part of the chain, and another broad signal (100±
125 ppm) was attributed to the ¯uorocarbon atoms.
The 29Si CP-MAS solid state NMR spectra of both gels
G-IVH and G-IVF are similar. Both spectra exhibit a sharp
resonance at 3 ppm, assigned to the central silicon (Si±Me)
atom and a broad signal centered at 63 ppm corresponding
to the T (:CSiO3) units. No signal is observed in the Q
(:SiO4) units region meaning that no carbon±silicon bond
cleavage occurred during gel formation.
sharp peaks, owing to the ¯exibility of the hydrocarbon
chain, at 50, 59 and 68 ppm, that of G-IIIF presents
broader overlapping peaks in the region 47, 67 ppm. The
broadness of the signal in Fig. 2b, is probably related to the
more rigid nature of the per¯uoroalkyl spacer, compared to
that of the hydrocarbon spacer. Moreover, G-IIIF seems a
more condensed material than G-IIIH since the T3 signal [:
C Si (OSi)3] ( 67 ppm) exhibits the highest intensity. The
hybrid network in G-IIIF has a higher degree of condensa-
tion than in G-IIIH and is also probably more rigid than the
hybrid network in G-IIIH.
2.2.3. Gels prepared from bis-silylated precursors with
pendant group
2.3. Properties of gels 1
The hydrolysis of the hydrogenated derivative IVH did
not lead to gel formation in ethanol but was successful in
THF to give gel G-IVH. The hydrolysis polycondensation of
IVF was performed in a 1/5 mixture of methanol/
C6F13C2H4OH and led to gel G-IVF (Scheme 6).
The gels G-IVH and G-IVF were characterised by 13C
CP-MAS NMR. The spectrum of G-IVH exhibits sharp
signals consistent with the molecular structure of IVH.
The signals centered at 3.5 and 0.5 ppm are assigned
to the carbon atoms bonded to the central silicon atom. The
sharp peaks at 14.3, 23.0, 24.0, 29.9, 32.3 and 34.0 ppm are
attributed to the carbon chain and the remaining two sharp
peaks at 18.5 and 58.1 ppm correspond to the carbon
atoms of residual uncondensed ethoxy groups at silicon.
The surface areas were determined by nitrogen absorp-
tion experiments according to BET [42]. The calculated
surface area from the adsorption±desorption isotherms are
given in Table 1. Most gels were non-porous materials and
showed very low surface areas ranging from 0.6 to
21.0 m2 g 1. Only the gel G-IIIF was a porous material
with a quite high surface area (300 m2 g 1).
For G-IIIF the adsorption/desorption isotherm plot exhi-
bits a hysteresis loop at high relative pressure, P/P0, con-
sistent with a mesoporous material. The BJH desorption dV/
d log (D) pore volume plot [44] showed a bimodal distribu-
Ê
tion of pores with average diameter in the region 30±35 A
Ê
and with larger mesopores over a wide range 100±400 A.
The pore structure of sol±gel prepared hybrid materials
has been shown to be strongly dependent on the reaction
conditions during gel formation and on the structure of the
precursor [31,43]. Bis-silylated precursors having a rigid
bridging spacer were, for example, shown to give highly
porous materials, whereas those with a ¯exible bridging unit
led to hybrid materials with low porosity. The high porosity
Table 1
BET surface areas (m2 g 1) of gels measured using N2 as sorption gas
G-IIH0 G-IIF0 G-IIH1 G-HF1 G-IIIH G-IIIF G-IVH G-IVF
2.3
0.6
1.9
21.0
5.9
300.6
0.8
1.1
Scheme 6. Synthesis of gels bearing pendant groups.

B. Ameduri et al. / Journal of Fluorine Chemistry 104 (2000) 185±194
189
Fig. 3. TGA-thermograms of: (a) G-IIH0 (- - -) and G-IIF0 (Ð); (b) G-IIH1 (- - -) and G-IIF1 (Ð); (c) G-IIIH (- - -) and G-IIIF (Ð); (d) G-IVH (- - -) and
G-IVF (Ð).
in gel G-IIIF probably results from the more rigid nature of
the per¯uoro-alkyl bridging spacer in precursor IIIF. Long
chain hydrocarbon spacers which are ¯exible, like in pre-
cursor IIIH, have been shown to yield a hybrid with low
porosity [43].
ments. The gels G-IIF0 and G-IIF1 showed a marked
thermostability. The thermal decomposition of G-IIF1 is
signi®cant above 4008C (versus 2008C for G-IIH1) and ends
at 5508C. The weight loss (65%) corresponds to the elim-
ination of the organic ¯uorocarbon moieties in the hybrid
material. The gel G-IIF0 behaves similarly. The gels G-IIH0
and G-IIH1 decomposed above 2008C up to 6008C to give a
33±38% weight loss associated with the elimination of the
hydrocarbon moieties. The thermal decomposition of the
¯uorinated gels starts at higher temperature and the weight
loss appeared more abrupt than for the hydrocarbon gels. A
different behavior was observed for the gels G-IIIF and G-
IVF (Fig. 3c and d).
The similar thermal stability was found for gels G-IIIF
and G-IVF for which decomposition started at a temperature
of 2308C, only slightly higher than the decomposition
temperature (2008C) for the analogous hydrocarbon hybrid
gel G-IIIH and G-IVH. At about 500±6008C respective
weight losses of 82 and 72% for ¯uorinated gels, and 56
and 43% for hydrocarbon gels corresponded to the elimina-
tion of the organic spacers. The behaviour of these hybrid
2.3.1. Pyrolysis of hybrid gels in air
It is well-known that ¯uorinated polymers can withstand
severe temperature conditions without being degraded [2,3].
For example, poly¯uoroalkylsilanes used as coating agents
proved to bring higher thermal stability to silicas [15]. This
led us to examine the thermogravimetric behaviour (TGA)
of the ¯uorocarbon gels and to compare them with the
hydrocarbon gels analogues. These analyses were per-
formed in an air ¯ow and the samples were heated at a
1
rate of 108C min from 20 to 12008C.
The thermograms of gels from G-II to G-IVare shown in
Fig. 3.
In most cases, the hybrid gels containing ¯uorocarbon
fragments exhibit a thermal stability signi®cantly higher
than that of the related gels containing hydrocarbon frag-

190
B. Ameduri et al. / Journal of Fluorine Chemistry 104 (2000) 185±194
materials may be related to the structure of the bis-silylated
precursors IIIH, IIIF, IVH and IVF and to the structure of the
resulting hybrid network in gel G-IIIH, G-IIIF, G-IVH and
G-IVF. Compared to hybrid gels G-IIH and G-IIF, having
pendant organic or ¯uoro-organic moieties, the structure of
the hybrid network is quite different. In gels G-II the
pendant group is more likely to be located at the surface
of the silica-based material [31,43], in some way coating the
material, and, therefore, a large in¯uence of the nature of the
organic fragment may be expected on the thermal stability.
In the case of gels G-III, owing to the structure of the bis-
silyl precursor the organic or ¯uoro-organic bridging spacer
is more likely to be embedded in the silica matrix [31,42].
Therefore, it may have a lower in¯uence on the thermal
stability and little difference can be seen in decomposition
temperatures between the hydrocarbon or ¯uorocarbon
hybrid gels. The ¯uorocarbon gel G-IVF, behaves similarly
to hybrid gel G-IIIF. This may be indicative of a similar
structure for the two gels, both arising from the hydrolysis of
bis-silylated precursors.
In summary, it appears that the presence of ¯uorocarbon
chains in the gels, no matter how they are introduced,
affords to these materials a higher thermal stability than
that of gels prepared from hydrocarbon precursors. The
highest gain in stability is observed in the case of the gels
prepared from the monosilylated precursors. The presence
of the ¯uorocarbon moieties at the surface of the material
may account for the behaviour of these materials, which
present a similar stability to that observed for ¯uorosilicones
[14,45].
These results are consistent with water and oil repellancy
brought by the ¯uorinated groups orientated on the surface
of the ®lm. The silica fragments, SiO1.5, probably have a
much better af®nity with the glassy substrate. It is worth
noting, that two behaviours were observed: the coatings
prepared from precursors C8F17(CH2)nSi(OMe)3 IIF or from
difunctional bis(trialkoxy)silanes IVF having a pendant
¯uorinated chain exhibit the highest contact angle values,
112 and 1088 for water, respectively. By contrast, a lower
contact angle (988 for water) was observed for the coating
obtained from the bis-silylated precursors IIIF having a
per¯uoroalkyl group as spacer between the two silicon
atoms.
The results are consistent with the observations concern-
ing differences in thermal stability as a function of the
structure of the precursors. The hybrid gel G-IIF which
shows the highest thermal stability also corresponds to the
one which shows the highest value for contact angles. These
observations are consistent with the assumption that ¯uor-
ocarbon moieties in the hybrid gel are likely to be at the
surface of the material. By contrast, the precursor IIIF
yielded the gel G-IIIF, in which the ¯uorocarbon spacer
is less likely to be at the surface as it shows the lowest
thermal stability and lowest contact angles.
This observation is in good agreement with a recent
investigation performed on the preparation of poly(¯uor-
oacrylates)deposited on glass [45]. Also it is consistent with
the usually enhanced surface properties of materials which
also contain ¯uorinated side chains: polyurethanes [12],
silicones [46,47] or poly[methyl¯uoroalkyl]-siloxanes
[48±50].
2.3.2. Hydrophobic properties
Thin ®lms of hybrid gels were prepared on glass slides by
spin coating of the solutions containing the hydrolysed
precursor. The contact angles of a drop of water (polar
¯uid) and diiodomethane (apolar ¯uid) on the ®lms were
determined and listed in Table 2.
3. Experimental section
3.1. General comments
Fluorinated vinylic or allylic monomers were prepared as
previously described [40], the former being produced by
ethylenation of per¯uoroalkyl iodides (n-C6F13I or n-
C8F17I) followed by dehydroiodination, while the latter
were obtained by radical addition of per¯uoroalkyl iodides
to allyl acetate, followed by deiodoacetalization. TBAF
(1.0 M solution in THF) was purchased from Aldrich.
C6F13C2H4OH was kindly provided by Elf Atochem.
After reaction, the products were worked up and analyzed
by gas chromatography (GC) using a Delsi apparatus
(Model 330) equipped with an SE 30 column, 1 mÂ1/
8 in. (i.d.). The nitrogen pressure at the entrance of the
column was maintained at 0.6 bar and the detector and
injector temperatures were 260 and 2558C, respectively.
The temperature programme was from 50 to 2508C at a
heating rate of 158C min 1. The GC apparatus was con-
nected to a Hewlett±Packard integrator (Model 3390) which
automatically calculated the area of each peak on the
chromatogram.
As expected, the contact angles observed for coatings
with ¯uorocarbon hybrid gels (98±1128 for water and 70±
1038 for CH2I2,) are higher than those determined for
coatings obtained with hydrocarbon hybrid gels (858 for
water and 608 for CH2I2,). In addition, Table 2 shows that in
all cases the values of the contact angles from water are
always higher than those obtained from diiodomethane.
Table 2
Contact angles (degree) of poly(fluoroalkylsilsesquioxanes) and poly
(hydrogenoalkylsilsesquioxanes) in water and diiodomethane
Sample
yH O ꢀꢁ†
yCH I ꢀꢁ†
2
2 2
G-IIF0
G-IIH0
G-IIF1
G-IIIF
G-IIIH
G-IVF
G-IVH
112Æ5
85Æ6
89Æ4
58Æ8
103Æ7
70Æ6
60Æ10
90Æ3
66Æ4
109Æ10
98Æ5
90Æ5
108Æ4
91Æ5

B. Ameduri et al. / Journal of Fluorine Chemistry 104 (2000) 185±194
191
The products were characterized by 1H, 13C and 19F NMR
spectroscopy all undertaken at room temperature. H and
123.7 (2F, CH2C3F6CF2); 124.0 (2F, CH2C4F8CF2);
124.5 (2F, CH2C5F10CF2); 127.2 (2F, CF3CF2). 29Si
NMR (CDCl3) d, 11.6 (s).
1
13C NMR spectra were recorded on Bruker AC 200, 250 or
MW 360 instruments, using deuterated chloroform as sol-
vent and with TMS as internal reference. The letters s, d, t, q,
and m designate singlet, doublet, triplet, quartet and multi-
plet, respectively. 19FNMR spectra were also recorded on
Bruker AC 200 or 250 instruments using deuterated chloro-
form with CFCl3 as internal reference. Coupling constants
and chemical shifts are given in Hertz and ppm, respec-
tively. Solid state NMR spectra of 13C and 29Si were
obtained with a Bruker FT-AM200 or FT-AM400 apparatus
with cross polarization and magic angle spinning techniques
(CP-MAS) and TMS as reference for the chemical shifts.
Nitrogen surface area measurements were performed
according to the BET method, at 77 K with a Micromeritics
Gemini 2375 equipment.
3.3. Synthesis of 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-
heptadecafluorodecyltrimethoxy-silane, IIF-0
In a two-necked round bottom ¯ask containing 50 g
(86 mmol) of 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptade-
ca¯uorodecyltrichlorosilane cooled in an ice bath and
equipped with a condensor and a dropping funnel was
added dropwise 8.3 g (259 mmol) of methanol. After com-
plete addition, the mixture was kept stirring at room tem-
perature. Afterwards the lower organic phase was collected
by means of a separating funnel and distilled yielding 48.9 g
(85.3 mmol) of IIF-0 as a colorless liquid. bpˆ75±808C/
1
0.5 mmHg. Yieldˆ99%. H NMR (CDCl3): d, 0.9 (m, 2H,
Thermogravimetry (TG) experiments were performed on
a STA 409TH Netszch apparatus. Approximately, 50 mg of
the powdered samples was used for each run with an air ¯ow
SiCH2); 2.3 (m, 2H, CF2CH2); 3.5 (s, 9H, OCH3). 19F NMR
(CDCl3) d, 81.8 (CF3, 3F); 115.5 (2F,CF2CH2); 122.5
(2F, CH2CF2CF2 ); 123.0 (2F, CH2CF2CF2); 123.7 (2F,
CH2C3F6CF2); 124.0 (2F, CH2C4F8CF2); 124.5 (2F,
CH2C5F10CF2); 127.2 (2F, CF3CF2). 29Si NMR (CDCl3)
d, 44.6 (s).
1
1
of 50 cm3 min and a heating rate of 108C min
.
Surface properties measurements were determined from
samples prepared by spin coating on microscope slides from
a liquid sol±gel solution, on a Karl Suss Technique SA
apparatus (CT60 model) with an acceleration of 2000 rpm, a
spinning speed of 200±500 rpm for 10±20 s. The contact
angle of a drop of polar (water) or nonpolar (diiodomethane)
liquid on the ®lm was measured with a Kruss G1 instrument,
at room temperature (238C) by means of the sessile drop
technique by micrometer drive G23. On each sample, at
least ®ve measurements were performed: the difference
from the average values was not more than 78. The measur-
ing liquids were doubly distilled water whose surface ten-
3.4. Synthesis of 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-
heptadecafluoroundecyltrichloro-silane, IF-1
In a similar experiment as above, 46.0 g (100 mmol) of
4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadeca¯uoroun-
decene, 16.3 g (120 mmol) of trichlorosilane and 100 ml of
the H2PtCl6 catalyst were shaken at 1108C for 19 h. After
the same work-up, the expected ¯uoroalkylsilane was dis-
tilled as a colorless liquid. bpˆ143±1468C/23 mmHg
1
1
(yieldˆ98%). H NMR (CDCl3): d, 1.5 (m, 2H, SiCH2);
sion at 238C was 72.0 mN m and methylene iodide was
1.9 (m, 2H, CH2CH2Si), 2.2 (m, 2H, CF2CH2). 19F NMR
1
67.0 mN m
.
(CDCl3): same as that of IF-1. 29Si NMR (CDCl3) d, 11.4 (s).
Elemental analyses were performed at the Service Central
d'Analyse (CNRS, Lyon).
3.5. Synthesis of 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-
heptadecafluoroundecyltrimethoxysilane IIF-1
3.2. Synthesis of 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-
heptadecafluorodecyltrichlorosilane, IF-0
As above, the methanolysis of the ¯uoroalkyltrichloro-
silane was performed with a three-fold excess of methanol
leading to expected IIF-1 in 99% yield. bpˆ108±1128C/
In a Carius tube (CT) were introduced 44.6 g (0.1 mol) of
3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadeca¯uorodecene,
16.3 g (0.12 mol) of trichlorosilane and 100 ml of a solution
of 10% H2PtCl6 in isopropanol. The CT was frozen in an
acetone/liquid nitrogen bath (Tˆ 808C) and sealed. It was
placed in the cavity of an aluminum block put in a shaking
oven (Tˆ100±1158C for tˆ19 h). After reaction, the CTwas
cooled to room temperature and then immersed in liquid
nitrogen and opened. The black liquid was passed over
alumina, the solvent evaporated and the ¯uoroalkyltrichlor-
osilane distilled giving 56.4 g (97%) of IF-0 as a colorless
liquid. bpˆ115±1188C/23 mmHg. 1H NMR (CDCl3): d, 1.7
(m, 2H, CH2SiCl3); 2.4 (m, 2H, CF2CH2). 19F NMR
(CDCl3) d, 81.8 (CF3, 3F); 115.5 (2F, CF2CH2);
122.5 (2F, CH2CF2CF2); 123.0 (2F, CH2C2F4CF2);
1
3
0.5 mmHg H NMR (CDCl3): d, 0.8 (t, JHHˆ8.0 Hz, 2H,
SiCH2); 1.7 (m, 2H, CH2CH2Si); 2.1 (m, 2H, CF2CH2); 3.5
(s, 9H, OCH3). 19F NMR (CDCl3) similar to that of IIF-0.
29Si NMR (CDCl3) d, 42.0 (s).
3.6. Synthesis of decyltrimethoxysilane, IIH-0
In a three-necked ¯ask, 7.1 g (50 mmol) of 1-decene,
7.32 g (60 mmol) of trimethoxysilane and 92.3 mg
(0.1 mmol, 0.5 mol%) of ClRh(PPh3)3 were dissolved in
20 ml of toluene and the mixture was heated to 1208C with
1
an oil bath. The reaction was monitored by H NMR and
was complete after 4 h. The solvent was removed in vacuo

192
B. Ameduri et al. / Journal of Fluorine Chemistry 104 (2000) 185±194
and the crude mixture was distilled to give 8.1 g (61%) of
IIH-0. bpˆ102±1068C/3.5 mmHg. 1H NMR (CDCl3): d, 0.6
(m, 2H, SiCH2); 0.8 (t, 3H, CH3); 1.1±1.4 (m, 16H, 8 CH2);
3.6 (s, 9H, O±CH3). 13C NMR (CDCl3) d, 9.1 (CH2Si); 14.0
(CH3); 22.5, 22.6, 29.2, 29.3, 29.5, 29.6, 31.9, 33.1 (8 CH2);
50.4 (OCH3). 29Si NMR (CDCl3) d, 41.3 (s).
dropwise a molar THF solution (70 cm3, 70 mmol) of
(EtO)3SiCH2MgCl [41]. After complete addition of the
Grignard reagent, the reaction mixture was left stirring
overnight at room temperature. The volatiles were pumped
off and hexane was added to the oily residue. The mixture
was ®ltered and hexane was evaporated in vacuo. The
remaining liquid was then distilled at reduced pressure
leading to a colorless liquid corresponding to bis(triethox-
ysilylmethyl)methylsilane (7.8 g, yieldˆ65%). bpˆ958C/
0.5 mmHg. 1H NMR (CDCl3): d, 0.0 (m, 4H, SiCH2); 0.2 (d,
3H, SiCH3); 1.2 (t, 18H, CH3); 3.8 (q, 12H, O CH2); 4.1
(m, 1H, Si H). 13C NMR (CDCl3) dˆ 4.5 (CH2Si); 3.5
(CH3Si); 18.2 (CH3CH2); 58.2 (OCH2). 29Si NMR (CDCl3)
dˆ 16.0 (Si H); 44.3 (Si O). Mass spectrometry (EI):
3.7. Synthesis of undecyltrimethoxysilane, IIH-1
The same procedure as above was applied with 6.16 g
(40 mmol) of 1-undecene, 6.1 g (50 mmol) of trimethox-
ysilane and 73.8 mg (0.08 mmol, 0.5 mol%) of ClRh(PPh3)3.
After distillation, 8.3 g (75%) of IIH-1 was obtained as a
colorless liquid. bpˆ92±948C/0.7 mmHg. 1H NMR(CDCl3):
d, 0.6 (m, 2H, SiCH2); 0.9 (t, 3H, CH3); 1.1±1.4 (m, 18H, 9
CH2); 3.6 (s, 9H, O±CH3). 13C NMR (CDCl3) d, 9.1
(CH2Si); 14.1 (CH3); 22.6, 22.7, 29.2, 29.3, 29.5, 29.6,
29.7, 31.9, 33.1 (9 CH2); 50.4 (OCH3). 29Si NMR (CDCl3)
d, 41.1 (s).
‡
‡
‡
M ˆ398 (7%), M 1 ˆ397 (24%), M Me ˆ383 (3%),
‡
M (EtO)3SiCH2 ˆ221 (100%). Elemental analysis calcd
for C14H38O6Si3: C, 45.18; H, 9.61. Found: C, 45.04; H,
9.89%.
3.10.1. Synthesis of bis(triethoxysilylmethyl)undecyl-
methylsilane, IVH
3.8. Synthesis of 1,10-bis(trimethoxysilyl)decane, IIIH
In a glass tube were introduced bis(triethoxysilylmethyl)-
methylsilane (3.98 g, 10 mmol), undecene-1 (1.68 g,
10 mmol) and H2PtCl6 (0.3 mol% from a solution of
10.7% Pt in isopropanol). The tube was sealed and was
heated in an oil bath at 1008C for 4 h. The black liquid was
®ltered and distilled. A colorless liquid was obtained (4.7,
83%). bpˆ1108C/0.1 mmHg. 1H NMR (CDCl3): d, 0.1 (s,
4H, SiCH2); 0.1 (s, 3H, SiCH3); 0.6 (m, 2H, SiCH2); 0.9 (m,
3H, CH3); 1.2 (t, 18H, CH3); 1.2 (m, 18H, CH2); 3.8 (q, 12H,
O CH2). 13C NMR (CDCl3) dˆ 3.4 (SiCH2Si); 0.8
(CH3Si); 14.1 (CH3CH2C); 17.5 (SiCH2); 18.2 (CH3CH2O);
22.7, 23.8, 29.3, 29.4, 29.5, 29.6, 29.7, 31.9, 33.8 (9CH2);
58.1 (OCH2). 29Si NMR (CDCl3) dˆ 43.5 (Si O); 1.9
(Si C). Elemental analysis calcd for C26H60O6Si3: C,
56.47; H, 10.93. Found: C, 56.04; H, 10.81%.
To a solution of ClSi(OMe)3 (34.4 g, 0.22 mol) and
magnesium chips (6 g, 0.25 mol) in 100 cm3 of THF cooled
in an ice bath was added 1,10-dibromo-octane (30 g,
0.1 mol) diluted in 100 cm3 of THF. After the addition
was complete, the reacting mixture was stirred at room
temperature for 12 h. The solvent was removed in vacuo and
the remaining sticky solid was extracted with hexane. The
mixture was ®ltered in order to eliminate the magnesium
salt. Hexane was pumped off and the liquid was distilled to
afford 26.7 g (70%) of IIIH as a colorless liquid. bpˆ143±
1448C/0.02 mmHg. 1H NMR (CDCl3): d, 0.55±0.65 (m, 4H,
SiCH2); 1.1±1.4 (m, 16H, 8 CH2); 3.5 (s, 18H, OCH3). 13
C
NMR (CDCl3) d, 9.1 (CH2Si); 22.6, 29.2, 29.5,33.1 (4 CH2);
50.4 (OCH3). 29Si NMR (CDCl3) d, 41.3 (s).
3.9. Synthesis of 1,10-bis(triethoxysilyl)-4,4,5,5,6,6,7,7-
octafluorodecane, IIIF
3.11. Synthesis of bis(triethoxysilylmethyl)-
4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-
(heptadecafluoroundecyl)methylsilane, IVF
4,4,5,5,6,6,7,7-octa¯uoro-1,9-decadiene(4 g,14.2 mmol),
HSi(OEt)3 (4.92 g, 30 mmol) and H2PtCl6 (0.3 mol% ) were
mixed in a Schlenk (v.c) tube. The stirred mixture was
heated for 6 h at 1208C and was monitored by 1H NMR. The
crude product was distilled yielding IIIF in 65%. bpˆ120±
1228C/0.015 mmHg. 1H NMR (CDCl3): d, 0.7 (t, 4H,
SiCH2); 1.2 (t, 18H, CH3); 1.6±1.8 (m, 4H, CH2); 1.9±
2.3 (m, 4H, CH2CF2); 3.8 (q, 12H, O±CH2). 13C NMR
(CDCl3) dˆ10.1 (CH2Si); 14.1 (CH2); 18.1 (CH3); 33.8 (t,
2JCFˆ22.6 Hz, CH2CF2); 58.4 (OCH2); 105±125 (m, CF2).
29Si NMR (CDCl3) dˆ 46.6 (s).
The same procedure as above was used. The dark brown
solution was ®ltered on celite to yield a viscous colorless
liquid (7.7 g, 90%). Attempt to distil the product resulted
in decomposition. 1H NMR (CDCl3): d, 0.1 (s, 4H,
SiCH2Si); 0.1 (s, 3H, SiCH3); 0.7 (m, 2H, SiCH2); 1.2 (t,
18H, CH3); 1.64 (m, 12H, CH2); 2.0 (m, 12H, CH2); 3.8 (q,
12H, O CH2). 13C NMR (CDCl3) dˆ 3.4 (SiCH2Si);
0.9 (CH3Si); 14.8 (CH3CH2C); 17.2 (SiCH2); 18.2
(CH3CH2O); 34.7 (CH2CF2); 58.1 (OCH2); 102±125
(8C±F). 29Si NMR (CDCl3) dˆ 44.1 (Si±O); 2.1 (Si C).
‡
3.10. Synthesis of bis(triethoxysilylmethyl)methylsilane
Mass spectrometry (EI): M Me ˆ843 (10%), M (EtO)3-
‡
‡
SiCH2 ˆ681 (40%), M C8F17C3H6 ˆ397 (71%). Ele-
mental analysis calcd for C26H43O6F17Si3: C, 36.39; H,
5.05; F, 37.64. Found: C, 36.62; H, 5.06; F, 37.46%.
To a stirred solution of dichloromethylsilane (3.45 g,
30 mmol) in THF (10 cm3) cooled in an ice bath was added

B. Ameduri et al. / Journal of Fluorine Chemistry 104 (2000) 185±194
193
3.12. Preparation of gels
above was applied with ethanol as solvent. 1.12 g of white
powder was obtained.13C CP-MAS NMR (d, ppm) 17.6,
34.6, 58 and 115.0. 29Si CP-MAS NMR (d, ppm) 47.2,
3.12.1. Typical procedure for the hydrolysis of R±
Si(OMe)3 and Si(OMe)4 (RˆC10H21, C11H23, C8F17C2H4,
C8F17C3H6): formation of gels
54.1, 60.8,and 67.1. N2 BET surface area: 300.6
1
m2 g
.
G-IIH0; G-IIH1; G-IIF0; G-IIF1
R-Si(OMe)3 (1 mmol) and Si(OMe)4 (5 mmol) were
mixed in 6 cm3 of methanol (RˆC10H21 and C11H23) or a
mixture of methanol and C6F13C2H4OH (RˆC8F17C2H4,
C8F17C3H6) as solvents (v/v: 1/10). Water (11.5 mmol) and
a catalytic amount of TBAF (0.1% mol with respect to
silicon) were added and the mixture was mixed for a while
and left to stand at room temperature until gelation took
place. After 2 days, the gel was washed with acetone and
ether, powdered and the remaining material was dried by
means of a vacuum pump.
3.12.1.7. Hydrolysis of (C11H23)SiMe[CH2Si(OEt)3]2:
formation of gel G-IVH. (C11H23)SiMe[CH2Si(OEt)3]2
(2 mmol) was diluted in 2 cm3 of THF. Water (6 mmol)
and a catalytic amount of TBAF (0.1% mol) were added and
the same procedure as above was performed. 318 mg of
white powder was obtained after drying. 13C CP-MAS NMR
(d, ppm) 3.5, 0.5, 14.3, 23, 29.9, 32.3 and 58.1. 29Si CP-
MAS NMR (d, ppm) 2.7 and 62.8. N2 BET surface area:
1
0.8 m2 g
.
3.12.1.8. Hydrolysis of (C8F17C3H6)SiMe[CH2Si(OEt)3]2:
formation of gel G-IVH. This gel was prepared as above
using a mixture of ethanol and C6F13C2H4OH as solvents
(v/v: 1/5). 587 mg of white powder was obtained after
drying.13C CP-MAS NMR (d, ppm) 0.7, 17.7, 36.5,
3.12.1.1. Characteristics of G-IIH0. 426 mg of white
powder was obtained. 13C CP-MAS NMR (d, ppm) 12.8,
23.0, 29.7, 32.4 and 50.5. 29Si CP-MAS NMR (d, ppm) 51,
58, 65 (T units), 94, 103, 110 (Q units). N2 BET
surface area: 2.3 m2 g
1
.
58.2 and 117.0. 29Si CP-MAS NMR (d, ppm) 2.7 and
62.8. N2 BET surface area: 1.1 m2 g
.
1
3.12.1.2. Characteristics of G-IIH1. 551 mg of white
powder was obtained.13C CP-MAS NMR (d, ppm) 13.9,
22.9, 29.9, 32.4 and 50.5. 29Si CP-MAS NMR (d, ppm) 49,
4. Conclusions
57, 64 (T units), 94, 102, 110 (Q units). N2 BET
surface area: 1.9 m2 g
1
.
Fluorocarbon-containing hybrid gels as well as their
hydrocarbon analogues were prepared from monosilylated
and linear or branched disilylated precursors via sol±gel
hydrolysis condensation in the presence of TBAF as the
catalyst. The properties of these gels were investigated. The
surface area and the porosity of almost all gels were very
low (0.6±5.9 m2 g 1). Only the hybrid gel produced from
the bis-silyl precursor containing a more rigid ¯uorocarbon
spacer yielded a mesoporous material with high surface area
(300 m2 g 1). Thermogravimetric analysis in air showed a
higher thermal stability for ¯uorocarbon hybrid gels. The
surface properties were also enhanced for ¯uorocarbon
hybrid gels, exhibiting higher hydrophobicity and oleopho-
bicity than those of hydrocarbon homologue gels. The best
results in terms of thermal stability and hydrophobicity were
observed for materials produced by sol±gel hydrolysis of
per¯uoroalkyl monofunctional trimethoxysilanes. The
results support the hypothesis that in this case the ¯uoro-
carbon moieties are more likely to be segregated at the
surface of the material than in the case of hybrids containing
a more rigid per¯uoroalkyl spacer.
3.12.1.3. Characteristics of G-IIF0. 396 mg of white
powder was obtained. 13C CP-MAS NMR (d, ppm) 0.7,
20±35, 50.4, 110±125. 29Si CP-MAS NMR (d, ppm) 59,
67 (T units), 102, 110 (Q units). N2 BET surface area:
0.6 m2 g
1
.
3.12.1.4. Characteristics of G-IIF1. 413 mg of white
powder was obtained. 13C CP-MAS NMR (d, ppm) 5±20,
25±35, 50.3 and 100±125. 29Si CP-MAS NMR (d, ppm)
58, 65 (T units), 102, 110 (Q units). N2 BET surface
area: 21 m2 g
1
.
3.12.1.5. Hydrolysis of (MeO)3Si- C10H20-Si(OMe)3:
preparation of G-IIIH. To a solution of (MeO)3Si±
C10H20±Si(OMe)3 (3 mmol) in methanol (3 cm3), water
(9 mmol) and TBAF (0.1% mol) were added. The
mixture was stirred and left to stand at room temperature
until gelation occurred. After 2 days the gel was washed
with acetone and ether, then powdered. The obtained
material was dried at 1008C, overnight, using a vacuum
pump. 876 mg of white powder was obtained. 13C CP-MAS
NMR (d, ppm) 12.5, 23.0, 29.8, 33.1 and 49.8. 29Si CP-MAS
References
NMR (d, ppm) 49.9, 58.8 and 67.9. N2 BET surface
1
area: 5.9 m2 g
.
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