Synthesis and some properties of silanes and siloxanes with 5,5,6,6,7,7,7-heptafluoro-4,4-bis(trifluoromethyl)heptyl substituents

Article abstract of DOI:10.1007/s11172-005-0105-y

Methods for syntheses of new polyfluorinated compounds, viz., silanes containing substituents CF₃CF₂CF₂C(CF ₃)₂(CH₂)₃ (R^F) at the silicon atom and 1,3,5-tris(R^F)-1,3,5-trimethylcyclotrisiloxane that can be used for the synthesis of fluorocontaining oligo- and polysiloxanes of different structure, were developed. The polymerization of cyclotrisiloxane in the presence of 1,3-divinyltetramethyldisiloxane gave linear oligomers, whose chain contain -(R^F)Si(Me)O- units.

Full text of DOI:10.1007/s11172-005-0105-y

Russian Chemical Bulletin, International Edition, Vol. 53, No. 10, pp. 2229—2232, October, 2004
2229
✾
Synthesis and some properties of silanes and siloxanes
with 5,5,6,6,7,7,7ꢀheptafluoroꢀ4,4ꢀbis(trifluoromethyl)heptyl
substituents
A. E. Shamaev, A. V. Ignatenko, and S. P. Krukovskyꢀ
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (095) 938 3558. Eꢀmail: yar@ioc.ac.ru
Methods for syntheses of new polyfluorinated compounds, viz., silanes containing substituꢀ
ents CF3CF2CF2C(CF3)2(CH2)3 (RF) at the silicon atom and 1,3,5ꢀtris(RF)ꢀ1,3,5ꢀtriꢀ
methylcyclotrisiloxane that can be used for the synthesis of fluorocontaining oligoꢀ and
polysiloxanes of different structure, were developed. The polymerization of cyclotrisiloxane in
the presence of 1,3ꢀdivinyltetramethyldisiloxane gave linear oligomers, whose chain contain
—(RF)Si(Me)O— units.
Key words: hydrosilylation, polyfluorinated silanes, fluorocontaining cyclosiloxanes,
fluorocontaining polysiloxanes.
The most part of studies in the field of organofluoꢀ
The synthesis of the most part of highly fluoriꢀ
silicon polymers are related to the investigation of oligoꢀ
and polysiloxanes containing γꢀtrifluoropropyl substituents
in side chains. They formed a basis for the production of
thermally, oilꢀ, and gasolineꢀresistant resins, lubricants,
chemically stable coatings, and electrically insulating maꢀ
terials.1 The fluorine content in these compounds does
not exceed 36.5%. At the same time, it is of great theoretiꢀ
cal and practical interest to create new organofluosilicon
oligomers and polymers of different structure with a higher
fluorine content. The works on the synthesis and study of
these compounds with bulky polyfluorinated linear alkyl
substituents CF3(CF2)nCH2CH2 at the silicon atom have
been carried out recently in Japan and USA.2,3
nated alkylsilanes and siloxanes is based on olefins with
linear perfluoroalkyl substituents CF3(CF2)nCH=CH2
(n = 3—6) obtained in moderate yields from perfluoroalkyl
bromides(iodides) and ethylene.4 To prepare alkylꢀ
silanes and siloxanes, we used alkene 1, which was synꢀ
thesized by the reaction of accessible and cheap hexaꢀ
fluoropropylene dimers CF3CF=CFCF(CF3)CF3 and
CF3C(CF3)=CFCF3CF3 with alkyl bromide in the presꢀ
ence of CsF.10—12
Alkene 1 was silylated with chlorosilanes 2a—c in the
presence of chloroplatinous acid to form, according to
1H NMR, silanes 3a—c 11 in ~100% yield (Scheme 1).
In this work, we describe the methods for syntheses
of silanes containing a 5,5,6,6,7,7,7ꢀheptafluoroꢀ4,4ꢀ
bis(trifluoromethyl)heptyl substituent (RF) at the silicon
atom and 1,3,5ꢀtris(RF)ꢀ1,3,5ꢀtrimethylcyclotrisiloxane
and related oligomers, the fluorine content in which exꢀ
ceeds 50%. In these compounds, the polyfluorinated subꢀ
stituent at the silicon atom contains a branched perfluoroꢀ
hexyl group. Therefore, based on the known data,5 we can
assume that the surface tension of the related siloxane
derivative would be lower than that for analogs with linear
perfluoroalkyl substituents. The calculated data6 show that
a polymer with an elementary unit —(RF)Si(Me)O— can
possess several valuable properties: low dielectric conꢀ
stant (2.19), refractive index (1.33), and surface tension
(17.9 mN m–1), which are much lower than those for the
known polysiloxanes with γꢀtrifluoropropyl substituents
at silicon.1,7
Scheme 1
a
2
1
b
1
2
c
0
3
x
y
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2133—2136, October, 2004.
1066ꢀ5285/04/5310ꢀ2229 © 2004 Springer Science+Business Media, Inc.

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Russ.Chem.Bull., Int.Ed., Vol. 53, No. 10, October, 2004
Shamaev et al.
The reaction of trichlorosilane 3с with excess triethyl
orthoformate afforded triethoxysilane 4 (Scheme 2).
hydrolyzate to 300—350 °C in the presence of 3—5 wt.%
KOH (Scheme 4).
Scheme 4
Scheme 2
i. 40 °C, 2 h
Monofunctional silanes are modifiers of the surface of
different materials, in particular, derivatives of organic
bases are most efficient.5 For this purpose, we synthesized
substituted morpholine 5 from dimethylchlorosilane 3a
Scheme 3).
Scheme 3
Cyclotrisiloxane 6 is a mixture of transꢀ and cisꢀisoꢀ
mers. The boiling points, weight of the isolated fracꢀ
tions of cyclotrisiloxane, and ratio of isomers in the fracꢀ
tions determined by GLC are presented in Table 1. It
can be assumed that cyclotrisiloxane 6 is enriched in
the transꢀisomer as in the case of cyclotrisiloxane
[CF3(CF2)3CH2CH2Si(Me)O]3 with linear nonafluoroꢀ
hexyl substituents.
Contact angles of wettability of surfaces of glass plates
treated with compounds 3a or 5 are 88—90° (water) and
76—77° (oil VMꢀ4).
As known, the hydrolysis of dichlorosilanes with alkyl
substituents at the silicon atom affords a mixture of linear
and cyclic siloxanes existing in a mobile equilibrium.13
The ratio between linear and cyclic siloxanes in the hydroꢀ
lyzate depends substantially on the temperature and subꢀ
stituent structure and is shifted completely, in the case of
bulky alkyl radicals, toward cyclic siloxanes.7 Individual
cyclosiloxanes isolated from the hydrolyzate have differꢀ
ent activities in polymerization. Of cyclosiloxanes with
fluorocontaining alkyl substituents, cyclotrisiloxane is
most active in polymerization,7 while cyclotetrasiloxane
[CF3(CF2)4CH2CH2Si(Me)O]4 with linear polyfluoroꢀ
alkyl substituents do not polymerize even at elevated temꢀ
peratures.16,17
Methyldichlorosilane 3b was hydrolyzed in ether in
the presence of excess water. A comparison of the signals
of siloxanes in the 29Si NMR spectra of the hydrolyzate
with the published signals of siloxanes14,15 and determiꢀ
nation of the ratio of their integral intensities showed
that the hydrolyzate contained 32% cyclotrisiloxane
[(RF)Si(Me)O]3 (two signals: –10.5 ppm and –10.7 ppm),
35% cyclotetrasiloxane [(RF)Si(Me)O]4 (three signals:
–21.1, –21.3, and –21.7 ppm), and 33% cyclic (with the
degree of oligomerization n > 4) and linear siloxanes (sigꢀ
nals: –13.7 ppm (HO(RF)Si(Me)O—) and –23.2 ppm
(—(RF)Si(Me)O—)).
Polymerization of 1,3,5ꢀtris(3,3,4,4,5,5,6,6,6ꢀnonaꢀ
fluorohexyl)ꢀ1,3,5ꢀtrimethylcyclotrisiloxane in the bulk
under the action of acids and alkalis has been studied
previously.16,17 In both cases, more thermodynamically
stable products were formed: cyclotetrasiloxane (74.3%)
Table 1. Boiling points, weights, and ratios of cisꢀ and transꢀ
isomers of cyclotrisiloxane 6 in fractions
Fraction
B.p./°C*
m/g**
cis/trans***
(% of load)
Forerun
101—132
30 (13.6)
1 : 2.2
fraction
1
2
3
4
5
132—137
137—143
144—148
148—152
152—155
16 (7.2)
10 (4.5)
26 (11.8)
18 (8.2)
42 (19.1)
1 : 2.9
1 : 3.7
1 : 4.4
1 : 4.9
1 : 5.5
* p = (2—8)•10–2 Torr.
We isolated cyclotrisiloxane 6 by continuous rectificaꢀ
tion from a mixture of siloxanes formed on heating the
** Weight of the fraction.
*** Ratio of isomers according to the GLC data.

Substituted silanes and siloxanes
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 10, October, 2004
2231
mined by GPC on a Bruker LC21 instrument (column IBM
GPC/SEC (10 µm, 300×7.7 mm), eluent flow rate 0.8 mL min–1
and higher cycles (n > 4). This is related to the fact that
depolymerization with the formation of higher cycles is
observed along with polymerization (siloxane chain
growth). We carried out the cationic polymerization of
cyclotrisiloxane 6 in the presence of 1,3ꢀdivinyltetraꢀ
methyldisiloxane 7 (molar ratio 7 : 1) and СF3SO3H as
catalyst. Oligomer 8 containing reactive vinyl groups at
the chain ends was obtained (Scheme 5).
,
trichlorotrifluoroethane as eluent, refractometer as a detector).
5,5,6,6,7,7,7ꢀHeptafluoroꢀ4,4ꢀbis(trifluoromethyl)heptꢀ1ꢀ
ene (1) was synthesized by somewhat modified procedure deꢀ
scribed previously.10 Anhydrous CsF (91.2 g, 0.6 mol), freshly
distilled diglyme (200 g, 1.2 mol), and a mixture of hexafluoroꢀ
propylene dimers (180.1 g, 0.6 mol) were placed in a threeꢀ
necked flask equipped with a stirrer with a mercuryꢀfree seal
under anhydrous argon. The reaction mixture warmed slightly.
Then allyl bromide (72.6 g, 0.6 mol) was added with vigorous
stirring for 2 h at 40 °C. After the reaction mixture was stored at
this temperature for 40 h, it was fractionated to three fractions
with boiling intervals of 67—110, 110—140, and 140—160 °C.
The first two fractions were combined and rectified on a column
of 1000×15 mm (spiral prismatic packing 3×3×0.2) with a reflux
ratio of 1 : 30, and the fraction with b.p. 107—113 °C was colꢀ
lected (226 g). According to GLC, the purity of the resulting
alkene 1 was equal to 96—97%. The 1H and 19F NMR spectra
corresponded to those presented in Ref. 12.
Scheme 5
Hydrosilylation of alkene 1 with chlorosilanes 2a—c (general
procedure). Compound 1 (180.05 g, 0.5 mol) was placed in a
twoꢀnecked flask equipped with a condenser with dry ice and a
dropping funnel, and argon was passed through the flask. One
droplet of a 10–2 М solution of H2PtCl6 in THF was added to
alkene 1 heated to 70 °C, and chlorosilane 2a—c (0.55 mol) was
slowly added dropwise with vigorous stirring. The reaction mixꢀ
ture was stirred at this temperature for 2 h, and the resulting
compounds 3a—c were isolated by fractionate distillation.
5,5,6,6,7,7,7ꢀHeptafluoroꢀ4,4ꢀbis(trifluoromethyl)heptylꢀ
methyldichlorosilane (3b) was synthesized from 1 and methylꢀ
dichlorosilane 2b in 89% yield (211.4 g), b.p. 50—51 °C (1 Torr).
Found (%): C, 25.56; H, 2.01. C10H9Cl2F13Si. Calculated (%);
C, 25.28; H, 1.91. 1Н NMR, δ: 1.58 (t, 2 H, СH2СH2CH2Si,
J = 8.0 Hz); 1.18 (m, 2 H, СH2СH2CH2Si); 0.37 (t, 2 H,
СH2СH2CH2Si, J = 7.8 Hz); 0.03 (s, 3 Н, СH3Si). 19F NMR, δ:
–64.49 (quintet, 3 F, (CF3)2СCF2, J = 11.1 Hz); –81.26 (t,
3 F, CF3СF2CF2, J =13.6—14.4 Hz); –107.95 (septet, 2 F,
CF3СF2СF2, J = 11.1 Hz); –123.72 (m, 2 F, CF3СF2СF2).
29Si NMR, δ: 31.1 (br.s).
i. Catalyst CF3SO3H, 100 °C, 20 h.
1
A comparison of the integral intensities of the Н sigꢀ
nals in the spectrum of the isolated oligomer showed that
the number of siloxane units in the middle of the chain was
1—0—12, which agrees well with the GPC data (Mn = 4790,
Mw =4960). Thus, we developed a method for the syntheꢀ
sis of polyfluorinated polysiloxane oligomers by the polyꢀ
merization of 1,3,5ꢀtris[5,5,6,6,7,7,7ꢀheptafluoroꢀ4,4ꢀ
bis(trifluoromethyl)heptyl]ꢀ1,3,5ꢀtrimethylcyclotrisilꢀ
oxane in the presence of 1,3ꢀdivinyltetramethyldisiloxane;
oligomers with terminal vinyl groups were obtained.
—
5,5,6,6,7,7,7ꢀHeptafluoroꢀ4,4ꢀbis(trifluoromethyl)heptylꢀ
dimethylchlorosilane (3a) was synthesized from 1 and dimethylꢀ
chlorosilane 2a in 86% yield (195.54 g), b.p. 76—79 °C (9 Torr).
Chemical shifts in the 19F NMR spectrum coincided within
measurement accuracy with the chemical shifts of the correꢀ
sponding groups in compound 3b. Found (%): C, 28.89; H, 3.38.
C11H12ClF13Si. Calculated (%); C, 29.05; H, 2.66. 1Н NMR, δ:
2.42 (t, 2 H, СH2СH2CH2Si, J = 8.0 Hz); 2.01 (m, 2 H,
СH2СH2CH2Si); 1.02 (t, 2 H, СH2СH2CH2Si, J = 7.8 Hz);
0.61 (s, 3 Н, СH3Si). 29Si NMR, δ: 29.09 (br.s).
5,5,6,6,7,7,7ꢀHeptafluoroꢀ4,4ꢀbis(trifluoromethyl)heptylꢀ
trichlorosilane (3с) was synthesized from 1 and trichlorosilane
2c in 90% yield (220.1 g), b.p. 81 °C (14 Torr). Chemical shifts
in the 19F NMR spectrum coincided within measurement accuꢀ
racy with the chemical shifts of the corresponding groups in
compounds 3a and 3b. 1Н NMR, δ: 2.11 (t, 2 H, СH2СH2CH2Si,
J = 8.0 Hz); 1.83 (m, 2 H, СH2СH2CH2Si); 1.24 (t, 2 H,
СH2СH2CH2Si, J = 7.8 Hz). 29Si NMR, δ: 10.4 (c).
Experimental
Hexafluoropropylene dimers were purchased from the Perm
Branch of the GIPKh (FOLꢀ62 Sort A; isomeric fraction of
hexapropylene dimers >99.8 wt.%, b.p. 46—51 °C). Allyl broꢀ
mide, 1,3ꢀdivinyltetraethyldisiloxane, and starting chlorosilanes
(Acros Organics, purity > 96 wt.%) were used without addiꢀ
tional purification. Diglyme was refluxed above CaH2 until gas
stopped evolving and then distilled. The catalyst was prepared
according to the following procedure: crystalline H2PtCl2•6 H2O
(1 g) was placed in THF preliminarily distilled above CaH2, and
the resulting solution was stored in a closed flask at room temꢀ
perature in the dark for 7 days.
1Н, 19F, and 29Si NMR spectra were obtained on a Bruker
ACꢀ200P spectrometer with a working frequency of 200 MHz
without a solvent using Me4Si (1Н, 29Si) and СFCl3 19F)
(
as external standards. GLC analysis was carried out on an
LKhMꢀ8MD chromatograph (column 1000×3.5 mm, carꢀ
rier Chromatone 0.160—0.200 mm with 5% Silicone SEꢀ30
(Chemapol)). The molecular weight of the oligomer was deterꢀ
4ꢀ{[5,5,6,6,7,7,7ꢀHeptafluoroꢀ4,4ꢀbis(trifluoromethyl)hepꢀ
tyl]dimethylsilyl}morpholine (5). Anhydrous morpholine (11.7 g,
0.14 mol) freshly distilled above CaH2 was slowly added to 3a

2232
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 10, October, 2004
Shamaev et al.
1
(30.3 g, 0.066 mol), resulting in the precipitation of white
morpholinium hydrochloride. The mixture was diluted with
Freonꢀ113 (50 mL), and the contents of the flask was vigorously
shaken and filtered. The solvent was removed from the filtrate
on a rotary evaporator, and compound 5 that formed was isoꢀ
lated by fractionation. The yield of 5 was 30.0 g (90%),
b.p. 94—96 °C (9 Torr). 1Н NMR, δ: 2.20 (br.s, 2 H,
СH2СH2CH2Si); 1.69 (br.s, 2 H, СH2СH2CH2Si); 0.55 (br.s,
2 H, СH2СH2CH2Si); 0.01 (br.s, 6 H, СH2СH2CH2Si(CH3)2);
Signals of the groups in the Н NMR spectrum of the oligomer
were assigned on the basis of the assignments of the signals of the
1
groups in the Н NMR spectra of the starting compounds, viz.,
1,3ꢀdivinyltetrasiloxane and cyclotrisiloxane. Н NMR, δ: 5.97
(br.s, CH2=CHSi); 2.26 (br.s, СH2СH2CH2Si); 1.85 (br.s,
СH2СH2CH2Si); 0.67 (br.s, СH2СH2CH2Si); 0.23 (s, СH3Si).
29Si NMR: –3.4 (CH2=CHSi(CH3)O); –23.7 (OSi(CH3)RFO).
1
The authors thank V. M. Kotov for help in experiꢀ
ments and discussion of some parts of the work.
2.43 (br.s,
4 H, N(СH2CH2)2O); 2.79 (br.s, 4 H,
N(СH2CH2)2O). 19F NMR, δ: –64.43 (m, 3 F, (CF3)2СCF2);
–81.29 (m, 3 F, CF3СF2CF2); –107.87 (m, 2 F, CF3СF2СF2);
–123.66 (m, 2 F, CF3СF2СF2). 29Si NMR, δ: 4.6 (s).
References
5,5,6,6,7,7,7ꢀHeptafluoroꢀ4,4ꢀbis(trifluoromethyl)heptylꢀ
triethoxysilane (4). Trifold excess triethyl orthoformate (44.4 g,
0.3 mol) was added to 5,5,6,6,7,7,7ꢀheptafluoroꢀ4,4ꢀbis(triꢀ
fluoromethyl)heptyltrichlorosilane 3с (49.5 g, 0.1 mol). The
mixture was heated at 40 °C for 2 h and then distilled. The yield
was 98% (46.7 g), b.p. 80—81 °C (1 Torr). Found (%): C, 33.74;
H, 4.03; F, 47.10. C15H21F13O3Si. Calculated (%); C, 34.36;
H, 4.04; F, 47.05. 1Н NMR, δ: 2.38 (t, 2 H, СH2СH2CH2Si, J =
7.8 Hz); 1.99 (br.s, 2 H, СH2СH2CH2Si); 1.00 (br.s, 2 H,
СH2СH2CH2Si); 4.00 (quintet, 6 Н, СH3CH2OSi, J = 7.1 Hz);
1.36 (t, 9 Н, СH3CH2OSi, J = 7.1 Hz). 19F NMR, δ: –64.43 (t,
3 F, (CF3)2СCF2, J = 11.1 Hz); –81.26 (t, 3 F, CF3СF2CF2,
J = 13.6—14.4 Hz); –107.84 (br.s, 2 F, CF3СF2СF2); –123.57
(br.s, 2 F, CF3СF2СF2). 29Si NMR, δ: –46.2 (s).
Hydrolysis of dichlorosilane 3b. Fourfold excess water was
added to 3b (240 g, 0.51 mol) in diethyl ether, and the mixture
was stirred at room temperature for 2 h. The ether layer was
separated and dried above MgSO4, the solvent was evaporated
in vacuo, and the residue was analyzed by 29Si NMR. A mixture
of siloxanes (220 g) was obtained. 29Si NMR, δ: –10.5, –10.7,
–21.1, –21.3, –21.7, –13.7, –23.2.
1,3,5ꢀTris(5,5,6,6,7,7,7ꢀheptafluoroꢀ4,4ꢀbis(trifluoromeꢀ
thyl)heptyl)ꢀ1,3,5ꢀtrimethylcyclotrisiloxane (6). The hydrolyzate
of disiloxane 3b (220 g) was loaded into a still of a rectification
column, KOH (6.5 g, 3 wt.%) was added, and the mixture was
heated to 300—350 °C. Rectification was carried out in a high
vacuum (2•10–2—8•10–2 Torr) on a column of 500×5 mm (spiꢀ
ral prismatic packing 3×3×0.2 mm) with a reflux ratio of 1 : 50.
The yield of trisiloxane 6 was 64% (142 g). Found (%): C, 28.42;
H, 2.25. C30H27F39O3Si3. Calculated (%): C, 28.58; H, 2.16.
1Н NMR of fractions 1—5 (mixture of cisꢀ and transꢀisomers),
δ: 2.26 (t, 2 H, СH2СH2CH2Si, J = 7.1 Hz); 1.82 (br.s, 2 H,
СH2СH2CH2Si); 0.67 (t, 2 H, СH2СH2CH2Si, J = 7.3 Hz); 0.21
(s, 3 Н, СH3Si). 29Si NMR of fractions 1—5, δ: –10.5, –10.7.
Polymerization of 1,3,5ꢀtris[5,5,6,6,7,7,7ꢀheptafluoroꢀ4,4ꢀ
bis(trifluoromethyl)heptyl)]ꢀ1,3,5ꢀtrimethylcyclotrisiloxane 6
in the presence of 1,3ꢀdivinyltetramethyldisiloxane. Cyclotrisilꢀ
oxane 6 (5 g, 0.0039 mol), disiloxane 7 (0.1063 g, 0.0006 mol),
and catalyst CF3SO3H (0.0022 g) were placed in an ampule
under dry argon. The ampule was sealed and placed in a thermoꢀ
stat at 100 °C. After 20 h, the ampule was opened, the contents
was dissolved in trichlorotrifluoroethane, and CaCO3 (0.5 g)
was added to the solution. The solution was filtered, and the
solvent was evaporated on a waterꢀaspirator pump. Siloxane was
washed with hexafluorobenzene, after which the benzene layer
was removed, and siloxane was dried in a highꢀvacuum setup.
Oligolymer 8 was obtained in 65% yield (3.3 g). All signals of the
groups in the 1Н NMR spectrum of the oligomer are broadened.
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Received April 6, 2004;
in revised form July 21, 2004