Original SF5-containing fluorinated copolymers based on vinylidene fluoride

Article abstract of DOI:10.1021/ma0512253

The radical co- and terpolymerization of fluorinated monomers bearing an SF₅ group, XYC= CZSF₅ (where X, Y, and Z represent either H or F atoms) with 1,1-difluoroethylene (vinylidene fiuoride, VDF or VF ₂) and hexafluoropropene (HFP), is presented. Although these SF ₅ monomers do not homopolymerize under radical initiation, they do copolymerize (and terpolymerize) in solution, in the presence of radical initiators with VDF (and with VDF and hexafluoropropylene (HFP)), hence leading to original copolymers bearing SF₅ side groups. NMR characterizations and yields enabled one to compare the relative reactivities of F ₂C=CFSF₅, HFP, perfluoromethyl vinyl ether, and perfluoropropyl vinyl ether in the copolymerization of VDF with these fluoroolefins. The degree of fluorine substitution on the ethylenic unit of the SF₅ monomers had an influence on their reactivity, on their relative incorporation in the copolymers, and on the molar masses of the resulting terpolymers - the higher the fluorine in the SF₅ monomer, the higher molecular weight. Interestingly, the greater the degree of fluorine substitution of the SF₅-containing monomer, the greater the yield of the reaction. The yield also increased as the amount of initiator was increased. The relative concentrations of the comonomers in each copolymer were assessed by ¹⁹F and ¹H NMR spectroscopy. The thermal properties (thermal stability and glass transition temperature) of these resulting SF ₅-containing fluoropolymers were also examined.

Full text of DOI:10.1021/ma0512253

8316
Macromolecules 2005, 38, 8316-8326
Original SF
Fluoride
5
-Containing Fluorinated Copolymers Based on Vinylidene
,†
,†
‡
‡
§
G. Kostov,* B. Ameduri,* T. Sergeeva, W. R. Dolbier, Jr., R. Winter, and
G. L. Gard§
Laboratory of Macromolecular Chemistry, UMR (CNRS) 5076, Ecole Nationale Sup e´ rieure de Chimie
de Montpellier, 8 rue Ecole Normale, 34296 Montpellier Cedex 05, France, Department of Chemistry,
University of Florida, PO Box 117200, Gainesville, Florida 32611-7200, and Department of Chemistry,
Portland State University, Portland, Oregon 97207
Received June 10, 2005; Revised Manuscript Received July 8, 2005
ABSTRACT: The radical co- and terpolymerization of fluorinated monomers bearing an SF
CZSF (where X, Y, and Z represent either H or F atoms) with 1,1-difluoroethylene (vinylidene fluoride,
VDF or VF ) and hexafluoropropene (HFP), is presented. Although these SF monomers do not
5
group, XYCd
5
2
5
homopolymerize under radical initiation, they do copolymerize (and terpolymerize) in solution, in the
presence of radical initiators with VDF (and with VDF and hexafluoropropylene (HFP)), hence leading
to original copolymers bearing SF
the relative reactivities of F CdCFSF
in the copolymerization of VDF with these fluoroolefins. The degree of fluorine substitution on the ethylenic
unit of the SF monomers had an influence on their reactivity, on their relative incorporation in the
copolymers, and on the molar masses of the resulting terpolymerssthe higher the fluorine in the SF
monomer, the higher molecular weight. Interestingly, the greater the degree of fluorine substitution of
the SF -containing monomer, the greater the yield of the reaction. The yield also increased as the amount
of initiator was increased. The relative concentrations of the comonomers in each copolymer were assessed
5
side groups. NMR characterizations and yields enabled one to compare
2
5
, HFP, perfluoromethyl vinyl ether, and perfluoropropyl vinyl ether
5
5
5
1
9
1
by F and H NMR spectroscopy. The thermal properties (thermal stability and glass transition
temperature) of these resulting SF -containing fluoropolymers were also examined.
5
Introduction
Usually, such fluoropolymers can be synthesized by
radical copolymerization of VDF with other fluoroalk-
enes leading to statistical copolymers7 except for
copolymers prepared from hexafluoroisobutylene10 (com-
mercialized by the Allied Company under the CMX
Fluoropolymers are of great interest because of their
unique combination of outstanding properties such as
,9
1
chemical inertness (to acids, bases, solvents, and petro-
leum), low dielectric constants and dissipation factors,
low water absorptivities, excellent weatherabilities, and
very interesting surface properties. Hence, these high
value added products can find relevant applications in
11
trade mark), methyl trifluoroacrylate, and R-trifluoro-
methyl acrylic acid,12 which are unexpected alternating
copolymers. In fact, VDF has been copolymerized with
various fluorinated monomers with the resulting co-
2
many fields of high technology: aeronautics, micro-
13
polymers bearing functions such as: hydroxy, ac-
electronics, engineering, chemical, and automotive in-
etoxy,1
3,14
thioacetoxy, sulfonyl fluoride, nitrile,
15
16
17
3
4
5
dustries, optics, textile finishing, and military use.
bromine,18 or a perfluoroalkyl group.
19
The specific properties (adhesion, solubility, curability,
surface properties, good hydrophilicity, heat or chemical
resistance) of a fluoropolymer are determined by the
nature of the specific functional group that is present
in the lateral position of the copolymer backbone. The
synthesis of fluoropolymers can be realized by copoly-
merization of fluoroalkenes with other fluorinated or
nonhalogenated monomers. In contrast to such copoly-
mers, fluorinated homopolymers (e.g., poly(vinylidene
fluoride), poly(tetrafluoroethylene), or polychlorotrifluo-
roethylene) exhibit a high crystallinity rate that induces
high costs in the processing at the molten state, poor
solubility in organic common solvents, and difficult
cross-linking.
Interestingly, monomers bearing the SF5 group have
led to a number of materials that can be used as high-
performance lubricants and optical materials, water
repellent and oil-resistant sealants, antifoaming agents,
surface-active agents, and protective surface coatings.2
Recent studies have prepared not only SF5-polyfluoro-
0-23
2
4
25
alkylacrylates, SF5-polyfluoroalkylsiloxanes,
SF5-
polyfluoroalkylepoxides26 but also aromatic polymers
that include polyimides containing the SF5(CF2)nC6H3-
26,27
groups (n ) 0, 2),
polyacrylate, and polystyrene
containing the SF5CF2CF2- group.28 Additional proper-
ties brought about by the SF5 group include low wet-
tability, low refractive index, low surface energy, high
dielectric strength, and high chemical and thermal
stability. The use of SF5 monomers has resulted in the
preparation of the first organic superconductor with an
organic anion,29 the first SF5-organic metals/organic
semiconductors,30 the first SF5-containing ionic liquids,
and the preparation of novel liquid crystals.32
Among these fluorinated copolymers, those incorpo-
rating vinylidene fluoride (VDF) monomeric units are
of particular interest, because they can be either ther-
6
7
1d,8
moplastics or elastomers or thermoplastic elastomers.
31
*
Corresponding authors. E-mail: georges.kostov@enscm.fr;
Different SF5-containing copolymers (acrylates, sili-
cones, epoxides) exhibit nonstoichiometric enrichment
of the film surface with fluorinated monomers bearing
SF5 groups.
bruno.ameduri@enscm.fr.
†
Ecole Nationale Sup e´ rieure de Chimie de Montpellier.
‡
§
University of Florida.
Portland State University.
1
0.1021/ma0512253 CCC: $30.25 © 2005 American Chemical Society
Published on Web 09/02/2005

Macromolecules, Vol. 38, No. 20, 2005
5
SF -Containing Copolymers 8317
Prior to our studies, in 1969 and 1974 Banks et al.33,34
reported the preparation of SF5-containing polymers
with VDF and HFP in emulsion using an aqueous redox
initiation system and perfluorooctanoic acid. However,
no data were supplied about the copolymer composi-
tions. In addition, the microstructure, the molecular
weight, and Tg values of copolymers obtained were not
described. We considered it to be worthwhile to revisit
that copolymerization system and to provide character-
ization of the binary and ternary systems with different
SF5 comonomers (hydrogenated and perfluorinated).
Hence, the objective of this paper deals with the
radical binary and terpolymerization of different SF5
containing monomers, their reactivity with VDF and
HFP, and the detailed characterization of the copoly-
mers obtained.
was bubbled vigorously through the solution for 5 min, after
which 3.2 g (0.020 mol) of SF Cl was bubbled into the mixture.
5
Triethylborane (1 mL) was then added dropwise to the
mixture, with stirring, and the bubbling of ethylene was
recommenced for another 5 min. After 1 h at -60 °C, the
solution was allowed to warm to -30 °C, where it was
maintained for another 2 h. The solvent was removed by
distillation to give 2.5 g (yield: 65%) of a residue that was
essentially pure 1-chloro-2-pentafluorosulfanylethane, which
1
was used directly in the next reaction: bp 92-93 °C; H NMR
1
9
δ 4.15-3.85 (m); F NMR δ 81.57 (q, 1F), 64.92 (d, 4F).
Another batch was carried out to get further amount with a
quasi-reproducible result.
2 5
Pentafluorosulfanylethene, M-I (H CdCHSF ). To 3.5
g of KOH in 4 mL of water was added 10.5 mL of 2-propanol
in a 50 mL three-necked flask equipped with an addition
funnel and a reflux condenser connected to a trap cooled by a
dry ice/acetone bath. The solution was brought to reflux, and
then 4.5 g (0.024 mol) of the 1-chloro-2-pentafluorosulfanyle-
thane was added dropwise. The mixture was refluxed for 2 h,
with 2.9 g (yield: 79%) of the desired product being collected
Experimental Section
Materials. Vinylidene fluoride (VDF), hexafluoropropene
HFP), and 1,1,1,3,3-pentafluorobutane were kindly provided
1
in the cooled trap: H NMR δ 5.74 (m, 1H), 6.01 (d, J ) 15 hz,
(
1
9
1
4
H), 6.68 (m, 1H); F NMR AB system, δ 81.5 (pent, 1F) and
by Solvay Solexis S.A., Tavaux, France, and Brussels, Belgium,
di-tert-butyl peroxide (DTBP) was obtained from Aldrich
Chimie, 38299 Saint Quentin-Fallavier, France, and trieth-
ylborane and 2-propanol were from Aldrich, Milwaukee, WI.
They were used as supplied. Acetonitrile, dimethyl sulfoxide,
ClSF , BrSF from Air Products, and methylene chloride of
5 5
analytical grade (Aldrich Chimie) were distilled over calcium
hydride prior to use.
3
5
5
9.7 (d, 4F), JAB ) 146 Hz.
-Chloro-1,1-difluoro-2-pentafluorosulfanylethane (Cl-
CH SF ). To a 50 mL three-necked flash bearing a dry
ice condenser and cooled to -50 °C was condensed 20 mL of
ClCF CH (Forane 142b) and 4.4 g (4 equiv) of CF dCH
VDF). To this mixture was added 2.7 g (0.017mol) of SF Cl.
Then 1.5 mL of Et B was added to the mixture dropwise, and
1
2
CF
2
5
2
3
2
2
(
5
3
the mixture was stirred at -20 to -30 °C for 3 h, after which
the flask was stoppered and allowed to stand at -20 °C for 3
days. Then the fluorinated solvent was evaporated, leaving
Analysis. The compositions of the co- and terpolymers (the
5
molar contents of VDF, HFP, and SF -containing monomers)
1
9
1
were determined by F and H NMR spectroscopy. The NMR
spectra were recorded on Bruker AC 200 and AC 250 instru-
ments, using deuterated acetone as the solvent and TMS (or
1
.5 g (40% yield) of almost pure product, 1-chloro-1,1-difluoro-
-pentafluorosulfanylethane, which was used directly in the
2
1
19
next reaction: bp 70 °C; H NMR δ 4.4-4.2 (m); F NMR δ
7.04 (q, 1F), 70.06 (d, 4F), -55.35 (s, 2F).
,1-Difluoro-2-pentafluorosulfanylethene, M-II (F
CHSF ). A 50 mL round-bottom flask equipped with a
1
19
3
CFCl ) as the references for H (or F) nuclei. Coupling
7
constants and chemical shifts are given in hertz and parts per
1
2
Cd
1
million, respectively. The experimental conditions for H (or
5
19
F) NMR spectra were as follows: flip angle 90° (or 30°),
magnetic stirrer and a 20 cm reflux condenser that was
connected to a cold trap (-78 °C) was charged with an aqueous
potassium hydroxide solution (13 g, 42.5 wt %). 1-Chloro-1,1-
difluoro-2-pentafluorosulfanylethane (4.4 g, 19 mmol) was
added at room temperature to the solution. The mixture was
slowly heated to 100 °C. Heating was continued for 2 h with
simultaneous collection of the product M-II in a cold trap, 2.1
acquisition time 4.5 s (or 0.7 s), pulse delay 2 s (or 5 s), number
1
9
of scans 16 (or 64), and a pulse width of 5 µs for F NMR.
Differential scanning calorimetry (DSC) measurements were
conducted using a Perkin-Elmer Pyris 1 instrument connected
to a microcomputer. The apparatus was calibrated with indium
and n-decane. After its insertion into the DSC apparatus, the
sample was initially cooled to -105 °C for 15 min. Then, the
1
19
g (13 mmol, 70% yield): bp 26 °C; H NMR δ 5.7 (m); F NMR
δ 78.89 (m, 1F, SF ), 72.78 (d, 4F, SF ), -65.80 (m, 1F), -83.96
-
1
first scan was made at a heating rate of 40 °C‚min up to 80
5
5
°
°
C, where it remained for 2 min. It was then cooled to -105
36-38
(
m, 1F).
,1,2-Trifluoro-2-pentafluorosulfanylethene, SF
(M-III). M-III was prepared from SF CHFCF Br as
-
1
C at a rate of 320 °C‚min and left for 10 min at that
1
2
5
CFd
temperature before a second scan was started at a heating rate
CF
5
2
-
1
of 20 °C‚min . Finally, another cycle was performed and a
38
described in the literature. The purity of the starting material
was checked via IR and NMR spectroscopy.
-1
third scan at a heating rate of 20 °C‚min was initiated, giving
the values of T
g
reported herein, taken at the half-height of
-1
IR (cm ): 1782 (s, CdC), 1351 (s), 1246 (s), 1089 (m), 898
the heat capacity jump of the glass transition.
(
vs), 862 (vs), 706 (m), 654 (wm), 613 (s). The absorptions at
Thermogravimetric analyses were performed with a Texas
-1
8
98 and 862 cm are due to S-F stretching while that at 613
Instrument TGA 51-133 apparatus in air at a heating rate of
-1
cm19 is due to one of the SF
5
deformation modes.
-
1
1
0 °C‚min from room temperature up to a maximum of 600
C.
Gel permeation chromatography (GPC) or size exclusion
chromatography (SEC) was carried out in tetrahydrofuran at
0 °C, at a flow rate of 0.8 mL/min, by means of a Spectra
F NMR (CDCl
3
, CFCl
3
): 69.7 (nine-line pattern, 1F, SF
5
);
°
5
9.0 (d, 4F, SF ); -163 (m, 1F, CF)); - 99.5 (m, 2F,)CF
5
2
).
Copolymerization. The batch copolymerizations of VDF
with CF dCFRf (Rf stands for CF , OCF , or SF ) were
2
3
3
5
3
performed in thick borosilicate Carius tubes (length 130 mm,
3
Physics Winner Station, a Waters Associate R 401 differential
refractometer, and a set of four columns connected in series:
Styragel (Waters) HR4 5µ, HR3 analyses 5µ, PL Gel (Polymer
Laboratories) 5µ 100 Å. Monodispersed (PMMA) standards
were used for calibration. Aliquots were sampled from the
reaction medium, diluted with tetrahydrofuran up to a known
concentration (Cp,t) ca. 4 wt %, filtered through a 20 µm PTFE
Chromafil Membrane, and finally analyzed by GPC under the
conditions described above.
10 mm i.d., thickness 2.5 mm; for a total volume of 8 cm ).
After the introduction of the initiator (di-tert-butyl peroxide
∼ 1.0 mol % versus the monomer quantities) and acetonitrile
(1.5-2.0 g), the tube was connected to a manifold and then
cooled with liquid nitrogen. After five freeze-thaw cycles, the
appropriate gas quantities were trapped in the tube cooled in
liquid nitrogen under 20 mmHg. To introduce the targeted
VDF quantities, a previous calibration was made to link the
gas pressure (bar) to the introduced weight (grams) (for
example, a difference of pressure of 0.66 bar represents 1.00
g of VDF). The tube was sealed while immersed in liquid
nitrogen and then stirred at the chosen temperature (140 °C)
for the required time (0.5 h was chosen for carrying out the
5
Synthesis of SF -Containing Monomers. 1-Chloro-2-
2 2 5
pentafluorosulfanylethane (ClCH CH SF ). A 50 mL three-
necked flask containing 30 mL of methylene chloride and
bearing a dry ice condenser was cooled to -60 °C, and ethylene

8318 Kostov et al.
Macromolecules, Vol. 38, No. 20, 2005
process of radical copolymerization). After reaction, the total
product mixture was analyzed by 19F NMR and H NMR. Then,
the copolymers were precipitated from cold pentane and dried
until constant weight was reached.
When we attempted to use this method for prepara-
tion of M-II, a messy mixture containing the product
as well as its decomposition products was obtained.
Winter and Gard successfully prepared M-II starting
from 1-bromo-1,1-difluoro-2-pentafluorosulfanylethane.37
Fortunately, the chloro precursor underwent dehydro-
chlorination smoothly under the same conditions with
no formation of decomposition products being observed
upon its treatment with 42.5% KOH solution.
1
Batch terpolymerizations of VDF with HFP and the SF
containing monomers were performed in a 160 mL Hastelloy
HC 276) autoclave, equipped with an inlet valve, a mano-
5
-
(
meter, and a rupture disk. The autoclave was purged with 20
bar of nitrogen pressure and left closed for 20 min to test for
leakage. After the pressure was released, a 20 mmHg vacuum
was operated for 15 min, and then the initiator di-tert-butyl
M-III monomer (F2CdCFSF5) was obtained from the
radical addition of BrSF5 onto trifluoroethylene followed
by a dehydrobromination as reported in a previous
work3
5
peroxide, SF monomers, and 1,1,1,3,3-pentafluorobutane were
introduced successively via a funnel tightly connected to the
introduction valve. Next, VDF and HFP were respectively
introduced by double weighing. The autoclave was then heated
at 143 °C for 5 h. After reaction, the vessel was cooled to room
temperature and then put in an ice bath. The nonreacted
monomers were released (from gaseous reactants) or separated
and the conversion vs monomers was determined. Then, the
solvent was evaporated, the terpolymer was precipitated from
cold pentane, and the total product mixture was dried at 0.1
mmHg at 40 °C for 15 h (to constant weight).
8,39
II. Radical Copolymerization of SF5-Containing
Monomers with VDF and HFP. II.1. Radical Co-
polymerization of F CdCFSF with VDF. Initially,
2
5
the radical homopolymerization of F2CdCFSF5 was
attempted under classic conditions of homopolymeriza-
tion starting from a di-tert-butyl peroxide [DTBP]0 to
[F2CdCFSF5]0 molar ratio of 2 mol %, 5.0 g (0.024 mol)
Highly viscous or rubber-like polymers were obtained.
of CF2dCFSF5, solvent 1,1,1,3,3-pentafluorobutane (70
wt %), temperature 143 °C, and reaction time 5 h. It
was noted that no reaction occurred, probably because
of the bulky SF5 substituent which, as in the case of
HFP, PPVE, PMVE, or PFP (1,1,3,3,3-pentafluoropro-
pene) prevents these fluoromonomers from undergoing
homopolymerizations.
Results and Discussion
I. Synthesis of Monomers Containing SF5 (SF-
5
M). Monomers M-I and M-II were prepared in a
manner similar to those described in the literature, but
39
using our new Et3B-initiation methodology to add SF5-
Cl to ethylene and VDF, respectively.
Then, the radical copolymerization of VDF with F2Cd
CFSF5 was carried out and compared to those of VDF
with hexafluoropropene (HFP), VDF with perfluoro-
methyl vinyl ether (PMVE), and VDF with perfluoro-
propyl vinyl ether (PPVE). For each couple, three
different copolymerizations were carried out using VDF
mole percentages of ca. 20, 50, and 75% under the same
batch conditions (initiator di-tert-butyl peroxide in
1
,1,1,3,3-pentafluorobutane as the solvent). Because of
the high volatilities of VDF and SF5-containing mono-
mers, the precise assessement of monomer conversions
was difficult to obtain. Nevertheless, the monomer
conversions were established to be less than 10 wt %.
Both comonomeric units in each of the copolymers
were assessed by 19F NMR spectroscopy.
The reaction of SF5Cl with ethylene proceeded
smoothly in dichloromethane at -30° to -20 °C over 2
h furnishing 1-chloro-2-pentafluorosulfanylethane in
good yield, but the synthesis of 1-chloro-1,1-difluoro-2-
pentafluorosulfanylethane proved to be more difficult.
Those of poly(VDF-co-HFP), poly(VDF-co-PMVE),19h,42
41
and poly(VDF-co-PPVE)1
9h,42
copolymers had been pre-
viously characterized by 19F NMR while that of poly-
(VDF-co-SF5M) copolymers has never been reported in
the literature (Table 1). For example, Figure 1 repre-
sents the 19F NMR of the copolymers prepared by
radical copolymerization of VDF and SF5 monomer III
(CF2dCFSF5) starting from an initial feed percentage
of VDF/M-III ) 70/30. This spectrum shows a peak
centered at about -91.1 ppm (noted I-91.1) characteristic
of the difluoromethylene groups of the head-to-tail VDF
chaining (i.e., normal VDF addition). Furthermore, a
series of other signals centered at -94.9 (noted I-94),
-113.7 (noted I-113.7), and -115.7 (noted I-115.7) ppm
can be assigned to the CF2 groups in (CH2-CF2)-(CF2-
CH2)-(CH2-CF2)-(CH2-CF2); -(CH2-CF2)-(CF2-
CH2)-(CF2-CH2)-; (CH2-CF2)-(CF2-CH2)-(CH2-
CF2) sequences, respectively, and correspond to the
4
0
As pointed out by Case et al., reactions of SF5Cl with
fluorocarbon olefins do not take place as easily as those
with hydrocarbon olefins. Thus, significantly harsher
conditions were required for the reaction with VDF to
occur. Only trace amounts of product were obtained
after treatment of VDF with SF5Cl in dichloromethane
or pentane. On the other hand, when the reaction was
carried out in ClCF2CH3 (Forane 142B) as a solvent, it
was possible to increase the yield up to 70-80%. Neat
Et3B instead of its 1 M solution in hexane was used for
these reactions, which allowed us to avoid a step of
solvent removal. Since the boiling point of ClCF2CH3 is
only -10 °C, essentially pure products were obtained
by simply warming the reaction to room temperature.
These chloro, pentafluorosulfanylethane intermediates
were used in the next step without further purification.
For the synthesis of pentafluorosulfanyl ethylene M-I,
43
reverse VDF addition (i.e., head-to-head addition) as
19
noted for the chemical shifts observed for F NMR
spectra of poly(VDF-co-HFP)4 or poly(VDF-co-PVME).
1,44
42
3
5
a method developed by Wessel et al. was adopted.
Treatment of the chloro precursor with KOH/H2O/i-
PrOH allowed preparation of monomer M-I in high
yields.
The multiplet signals from +75 to +50 ppm are ideally
an AB4 system and are assigned to the five fluorine
atoms in the SF5 groups; the first one was a nine-line
pattern, each line split into a triplet, and the

Macromolecules, Vol. 38, No. 20, 2005
Table 1. Comparative Study of Different Reactivities of VDF with Various Monomers in Radical Copolymerizationa
mol % monomer in the feed mol % monomer in the copolymer
5
SF -Containing Copolymers 8319
run no.
VDF
HFP
PMVE
PPVE
-SF
5
VDF
HFP
PMVE
PPVE
-SF
5
1
2
3
4
5
6
7
8
9
21.6
49.5
75.0
20.0
50.8
78.9
20.4
50.1
70.1
20.0
49.6
69.8
78.4
50.5
25.0
53.4
78.1
89.3
61.8
73.6
85.5
57.0
73.0
74.6
81.2
83.6
86.4
46.6
21.9
10.7
80.0
49.2
21.1
38.2
26.4
14.5
79.6
49.9
29.9
43.0
27.0
25.4
1
1
1
0
1
2
80.0
50.4
30.2
18.8
16.4
13.6
a
No homopolymerization of CF2dCFSF5 monomer.
Figure 1. 19F NMR spectrum of VDF/CF
dCF(SF ) copolymer at 70/30 mol % monomer ratio in the feed.
2 5
Table 2. 19F NMR Assignments of Fluorinated Groups in
the Poly(VDF-ter-HFP-ter-CF2dCFSF5) Terpolymers
Recorded in Deuterated Acetone
second one was a skewed doublet of a pentet. The
difluoromethylene group of VDF adjacent to CF2CF(SF5)
leads to a signal centered at -109.8 ppm while those
centered at -118.8 and -136.7 ppm are related to the
chemical
shift (ppm)
integrals
in eq 1,3
structure
-
CF2 and -CF groups, respectively, deriving from the
-71.2
-74.8
-91.1
-94.9
-CH2CF2CF2CF(CF3)-CF2-CH2-
-CH2-CF2-CF2-CF(CF3)-CH2-CF2-
-CF2-CH2-CF2-CH2-CF2-
I-71.2
I-74.8
I-91.1
I-94.9
perfluorovinyl group of the M-III monomer (Table 2).
The microstructure of the copolymers was assessed by
mol % SF5 ) (I+50to+75)/5 for the multiplet centered at
(CH2-CF2)-(CF2-CH2)-(CH2-CF2)-
-135 ppm for -CF(SF5) fluorine atom. Indeed, both
(
CH2-CF2)
fluorine atoms in the difluoromethylene group adjacent
to -CF(SF5) were anisochronous, hence leading to an
AB system. This arises from the bulky -SF5 group
which stiffens the molecule as we had noted in C4F9-
CF2CF(CF3)I obtained by telomerization of HFP with
-
108
-CH2CF2CF2CF(SF5)-
I-108
-110.1
-113.7
-113.8
-115.7
-118.8
-(CH -CF )CF CF(CF )-
2
2
2
3
I-110.1
I-113.7
I-113.8
I-115.7
-(CH2-CF2)-(CF2-CH2)-(CF2-CH2)-
-CF2CH2(CH2-CF2)-[CF2-CH2]-
-(CH2-CF2)-(CF2-CH2)-(CH2-CF2)-
-CH CF CF CF(SF )-
4
5
I-118.8
C4F9I. In that monoadduct containing a bulky iodine,
the central CF2 group yielded an AB system. This AB
system was also noted on CF2 of VDF adjacent to -CF2-
CF(CF3) as in the case of C3F7CF2CF(CF3)I. Because of
the overlapping of different signals in that region, it was
difficult to assess the mol % SF5M from δ CF2 atoms.
Interestingly, no doublet of multiplets centered at
2
2
2
5
-
-
-
119
136.7
183.5
-CH2CF2-CF2CF(CF3)-
-(CH2-CF2)-[CF2-CFSF5]-
-CH2CF2CF2CF(CF3)-
I-119
I-136.7
I-183.5
was observed, proving the absence of transfer reac-
tion.4
1,43-45
The mole percentage of VDF in the copoly-
mer was assessed from the following formulas taking
into account that integrals of signals centered at -113
-114.8 ppm corresponding to the -CH2CF2H end group

8320 Kostov et al.
Macromolecules, Vol. 38, No. 20, 2005
Figure 2. 1H NMR spectrum of VDF/CF
dCF(SF ) copolymer at 70/30 mol % monomer ratio in the feed.
2 5
•
•
•
and-116 ppm are the same with some overlapping of
those centered at -116 and -118.8 ppm:
R + H CdCF f RCH C F + RCF C H
2
(4)
2
2
2
2
2
R ) CH , t-BuO
3
mol % VDF ) [I-91 + I-94 + I-107 + 2I-113.7]/[I-91
+
1H NMR provides evidence of these hydrogenated end
groups as follows: CH3CH2CF- at 1.2 ppm, CH3CF2-
CH2- at 1.18 ppm, (CH3)3C-OCH2CF2- at 1.1 ppm,
and (CH3)3C-OCF2CH2- at 1.15 ppm. In addition,
signals of small intensities are observed in the 19F NMR
spectra at -60 and -65 ppm. They are assigned to CF2
of (CH3)3C-OCF2CH2- and confirm previous works
I-94 + I-107 + 2I-113.7] + 2I-136.7 (1)
1H NMR spectrum (Figure 2) exhibits one multiplet
signal centered at 3.0 ppm assigned to the -CH2 protons
of normal VDF units and traces of signals at 2.3-2.4
ppm that can be related to the CH2 groups in the reverse
4
1,43
structure of VDF (or tail to tail addition).
Interest-
•
dealing with the addition of t-BuO onto the CF2 site of
ingly, no triplet of triplets is seen, which would be
characteristic of -CH2CF2H arising from an H-transfer
from solvent or polymer.
4
3d
16f
VDF or onto the CF2 site of PMVE.
Both 19F and H NMR spectra were used to assess
the molecular weight of poly(VDF-co-SF5M-III) copoly-
mers
1
Table 1 summarizes the results obtained from the four
different series of radical copolymerization involving
VDF. It is observed that comparing all cases, the SF5
monomer is the least reactive and the following decreas-
ing reactivity series is suggested
NVDF ) [(I2.3-2.5 + I2.8-3.2)/2]/[(I1.2 + I1.8)/6] (5)
where NVDF is number of VDF units in copolymer and
Ii values are the integrals of H signals at given ppm,
assuming recombination of macroradicals as a main
HFP > PPVE g PMVE > SF M
(2)
5
1d
termination reaction.
That low reactivity of SF5M may arise from both the
bulky electron-withdrawing SF5 groups and the delo-
19
F NMR spectra yield the SF5/VDF molar ratio R in
the copolymer. Hence, the molecular weights can be
deduced from the following equation
•
calization of the electron in the radical ∼CF2C F(SF5)
terminal groups. This observation results in low molec-
ular weight copolymers in the range of 1700-5400
g/mol. From a mechanistic point of view, when DTBP
is thermally decomposed two different radicals can be
produced as follows
M ) 64N
+ 208RNVDF + 30
(6)
n
VDF
Table 3 lists the molecular weights of binary poly-
VDF-co-SF5M-III) copolymers obtained from eq 6.
In addition the solution polymerization used leads to
lower molecular weights in contrast to polymerizations
carried out in aqueous media (such as emulsion, mini-
emulsion, or suspension) that result in higher molecular
weights (as for poly(VDF-co-HFP) copolymers).1
(
•
•
t-BuO-O-t-Bu f 2t-BuO f 2 CH + 2CH COCH
3
3
3
(3)
,5,7c,9a
T > 100 °C
Hence, because of the difficulty to introduce an SF5
comonomer into a copolymerization, we have found it
worthwhile to carry out terpolymerizations of VDF,
HFP, and different SF5-containing monomers, M-I, M-II,
M-III, since it is known that the presence of HFP can
•
It is assumed that t-BuO undergoes a thermal frag-
•
43d
mentation (T > 100 °C) to generate CH3. The radicals
produced can react onto both sides of VDF in a nonre-
gioselective manner

Macromolecules, Vol. 38, No. 20, 2005
5
SF -Containing Copolymers 8321
5
Figure 3. Radical terpolymerizations of SF monomers with VDF and HFP.
Figure 4. 19F NMR spectrum of VDF/HFP/SF
(M-I) terpolymer at initial monomer ratio in the feed 72.0/19.4/8.6 mol %.
5
Table 3. Molecular Weights of Poly(VDF-co-SF5MIII) and
out in a high-pressure autoclave at 143 °C for 5 h using
di-tert-butyl peroxide as the radical initiator and 1,1,1,3,3-
pentafluorobutane as the solvent (Figure 3). Upon
completion of the reaction, the solvent was evaporated
and, after precipitation and drying, the products were
1
Poly(VDF-ter-HFP-ter-SF5Mi) Copolymers Assessed by H
1
9
and F NMR Analyses
molar ratio in
b
feed, mol %
copolymers
exp
Mn
(g/mol)
a
1
19
no.
VDF SF5Mi HFP NVDF
R
R1
R2
characterized by their H and F NMR spectra, which
allowed characterization of the microstructures of these
terpolymers. Depending on the identity of the SF5-
containing monomer and of the initial molar ratios,
three different types of terpolymers were obtained: (a)
a brown high viscous liquid oligomer (I) when using the
SF5 monomer M-I, which bears three H atoms on the
vinyl group; (b) a brown rubber-like polymer (II) when
using SF5 monomer (M-II); and (c) a gray rubber-like
polymer (III) when using the perfluorinated monomer
M-III. Regarding solubilities of the polymers, all of them
were soluble in acetone, THF, and 1,1,1,3,3-pentafluo-
robutane, whereas terpolymer III, based on the perflu-
orinated SF5 monomer, was also soluble in dichlo-
romethane and partially in chloroform. It was also noted
that the higher the fluorine content of the SF5 comono-
mer, the higher the yield of the reaction, and the higher
the initiator concentration, the greater the yield (Table
1
2
3
4
5
6
7
20.0
49.6
69.8
72.0
75.2
73.1
71.1
80.0
50.4
30.2
8.6
15 0.23
16 0.20
55 0.16
35
1750
1740
5350
4900
19.4
16.1
18.3
15.3
0.16 0.25
8.7
130
0.17 0.03 12400
0.21 0.07 16900
8.6
13.6
154
65
0.17 0.11
7300
a
Experiments 1-3 concern runs 10-12 in Table 1. Experiments
b
4
-7 concern experiment numbers in Table 4. R ) mol % SF5M-
III/mol %VDF in copolymer, R1 ) mol % HFP/mol % VDF in
terpolymer; R2 ) mol % SF5M-I/mol % VDF in terpolymer.
enhance the reactivity of VDF and of the comonomer
as recently reported in the case of F2CdCFO-C6H4-
Br. This is the case when one reactive couple of
monomers can involve the third low-reactive monomer
in terpolymerization.
II.2. Radical Terpolymerization of SF5-Contain-
ing Monomers with VDF and HFP. The expected
terpolymers should contain an increased amount of
fluorine in the polymer backbone (compared to the usual
level of incorporation of HFP), which should improve
the physicochemical properties of the resulting fluo-
ropolymers.
4
4
4
).
On the basis of such analyses, it was concluded that
in all cases statistical terpolymers were obtained wherein
the different monomeric units were randomly distrib-
uted in the backbone, and where microblocks of oligo-
(VDF)s could be noted in the terpolymer. The relative
A series of terpolymerizations were performed using
an initial [initiator]0/[total monomers]0 molar ratio of
1%. These radical-initiated polymerizations were carried
amounts of the monomers in the terpolymers were
assessed by 1 F NMR spectroscopy (Figures 4 and 6).
In addition, all 1H NMR spectra (Figures 5 and 7)
9

8322 Kostov et al.
Macromolecules, Vol. 38, No. 20, 2005
Figure 5. 1H NMR spectrum of VDF/HFP/SF
5
(M-I) terpolymer I at initial monomer ratio in the feed 72.0/19.4/8.6 mol %.
Figure 6. 19F NMR spectrum of VDF/HFP/SF
3.1/18.3/8.6 mol %.
(M-III) terpolymer III recorded in deuterated acetone at initial monomer ratio
5
7
exhibit signals that can be assigned to the methylene
groups of VDF units adjacent to difluoromethylene
groups in the 2.5-3.5 ppm range (with the high amounts
of VDF units in the terpolymer, small amounts of head-
to-head addition can also be seen, which gives rise to
signals at about 2.2-2.4 ppm). The low intensity of the
signals and absence of any triplet of triplets and of
doublet of multiplets centered at 6.3 and 5.6 ppm,
assigned to -CH2CF2H and CF2CFHCF3, respectively,
gave evidence that very little (Figure 5) or no (Figure
polymerizations in solution with organic initiators of
SF5-containing monomers such as M-I, M-II, and M-III,
have not been previously reported in the literature. The
main goal of this part was thus to identify those peaks
characteristic of such comonomers in the terpolymers.
In contrast, the determination of the various NMR
signals deriving from VDF and HFP units in co- and
terpolymers has been the subject of various
7,16f,41,44,46
papers.
The 19F NMR spectra of polymers I and III (Figures
4 and 6) as well as polymer II exhibit the characteristic
signals centered at -91, -94, -109, -110, -113.7, and
-116 ppm assigned to the difluoromethylene groups of
7
) chain transfer reaction occurred.
II.2.1. Determination of the Terpolymer Com-
19
positions by Using F NMR Spectra. Radical ter-

Macromolecules, Vol. 38, No. 20, 2005
5
SF -Containing Copolymers 8323
Figure 7. 1H NMR spectrum of VDF/HFP/SF
73.1/18.3/8.6 mol %.
(M-III) terpolymer III recorded in deuterated acetone at initial monomer ratio
5
VDF in the normal addition, adjacent to a F2CdCFSF5
unit, and to reverse addition: -CH2CF2-CF2CH2-CH2-
CF2- and -CH2CF2CF2CH2-CH2CF2-, respectively,
as observed in NMR spectra of copolymers (Table 2).
The signals located at -109.8 ppm (noted I-109.8) and
The integrals in the 19F NMR spectra (denoted above)
allow the determination of the molar fractions of VDF,
HFP, and SF5M units in the terpolymers, and they are
given by the following equations (eq 7):
43
-
110.1 (noted I-110.1) range are assigned to the difluo-
I
J
mol % of VDF in the terpolymer )
×
romethylene groups of the VDF unit adjacent to SF5M
and HFP unit, respectively.
I + I + I
J
K
L
1
00 (7a)
In addition, the chemical shifts centered at -71.2
(noted I-71.2), -74.8 (noted I-74.8) are assigned to the
IK
trifluoromethyl side group of HFP in the terpolymer:
CH2CF2CF2CF(CF3)-CF2-CH2-, -CH2-CF2-CF2-
CF(CF3)-CH2-CF2-, while those centered at -118.8
mol % of HFP in the terpolymer )
×
I + I + I
-
J
K
L
100 (7b)
(
noted I-118.8) and -183.5 (noted I-183.5) ppm are at-
tributed to the HFP difluoromethylene groups in -CH2-
CF2CF2CF(CF3)- sequences and to the tertiary fluorine
IL
I + I + I
mol % of SF5M in the terpolymer )
×
4
1
J
K
L
in CF2CF(CF3) of HFP, respectively.
1
00 (7c)
Finally, the multiplets centered at -114.0 ppm (noted
I-114.0) and -112.0 ppm (noted I-112.0) are attributed to
the difluoromethylenes of the SF5M unit in terpolymers
III and II, -(CF2-CF(SF5))- and CF2-CH(SF5))-,
respectively. Also, the peaks located in the -137.6 ppm
region (noted I-137) are assigned to the tertiary fluorine
atom in the CF group of -(CF2-CF(SF5))- monomer
unit in polymer III. The multiplets centered at +55 and
where
I-91.1 + I-94.9 + I-109.8 + I-110.1 + 2I-115.7
IJ )
(8a)
2
I-71.2 + I-74.8
I )
or I ) I-119/2
(8b)
(8c)
1
9
K
K
+
75 ppm in the F NMR are consistent with the
3
presence the SF5 group. The SF5 group, as found by
4
7
Muller et al., contains four magnetically equivalent
and one nonequivalent fluorine atoms (AB4 system). The
equatorial, A4, resonance is split into a doublet while
the apex, A, resonance is grossly a pentet with a “fine
IL ) I+50to+75/5 or I ) I
L -135
The degrees of incorporation of each monomer in the
terpolymers are listed in Table 4.
II.3. Characterization of the Terpolymers. Table
4 lists the final molar percentages of each termonomer
and also the molecular weights and thermal properties
of each terpolymer.
4
8
structure”. Cross et al. reported that the compounds
in which the SF5 group is bound to aliphatic hydrocar-
bons, a very intense broad band centered on or about
70 cm is found. They assigned this to the S-F
stretching modes. We observed the same behavior with
our compounds.
-
1
8
In the same experimental conditions (experiments I,
II, and III: terpolymer VDF/HFP/SF5M, starting from

8324 Kostov et al.
Macromolecules, Vol. 38, No. 20, 2005
Table 4. Monomer-Polymer Compositions of Poly(VDF-ter-HFP-ter-SF5M) Terpolymers and Their Main Characteristicsa
terpolymers
feed (mol %)
HFP
(mol %)
HFP
exp no.
Y
M
n
T
g
monomer
VDF
72.0
SF
5
M
VDF
71.0
SF
5
M
(wt %)
(g/mol)
PDI
2.0
(°C)
b
polymer I
19.4
16.1
18.3
15.3
8.6
8.7
11.6
14.1
16.4
13.5
17.4
2.1
45.0
52.2
72.5
91.2
2540
-50
H CdCH(SF )
2 5
b
polymer II
5
CdCH(SF )
b
75.2
73.1
71.1
83.8
78.3
78.1
8290
10030
6650
2.3
2.4
2.4
-41
-40
-50
F
2
polymer III
CdCF(SF
8.6
5.3
F
2
5
)
c
polymer IV
CdCF(SF
13.6
8.3
F
2
5
)
aReaction conditions: initiator DTBP, 1 mol %; solvent pentafluorobutane, 70 wt %; 143 °C; 5 h. Polymer solubility: soluble in acetone,
THF, C4F5H5; polymers I and II not soluble in CHCl3 and CH2Cl2 whereas polymers III and IV are soluble in CH2Cl2 and partially in
b
c
CHCl3. DTBP concentration 1 mol %. DTBP concentration 3 mol %.
Figure 8. SEC Chromatograms of poly(VDF-ter-HFP-ter-SF
5 5
M) terpolymers. Terpolymer compositions of VDF/HFP/SF M in
mol %: I, 71.0/11.6/17.4; II, 83.8/14.1/2.1; III, 78.3/16.4/5.3; IV, 78.1/13.5/8.3.
the same SF5M feed molar percentages of ca. 8.6 mol %
led to copolymers containing 17.4, 2.1, and 5.3 mol. %,
respectively (Table 4)). The increasing mole percent of
SF5M in feed makes increases in its mole percent in the
terpolymer and the yield. Usually, the final molar
percentages of VDF are higher than the molar percent-
ages in feed. As a matter of fact, this result is evidence
of the presence of oligo(VDF) blocks separated by one
SF5 monomeric unit in the terpolymer. The poor reac-
tivity of F2CdCH(SF5) monomer is not surprising when
In all cases, the SEC chromatograms (Figure 8)
showed one main maximum with two shoulders. This
can be surprising for terpolymers for which monomodal
distribution is expected, although more detailed experi-
ments are required to be done. The value of the average
molecular weights, M , of poly(VDF-ter-HFP-ter-SF5M)
n
terpolymers (experiments I, II, and III with ca. 8.6 mol
%
in feed of fluorinated SF5 monomer) or poly(VDF-ter-
HFP-ter-SF5M) terpolymers (experiment IV), 13.6 mol
%
in feed of perfluorinated SF5 monomer) were about
49
its behavior is compared to that of F2CdCH(CF3), PFP
-1
2
540, 8290,10030, and 6650 g‚mol , respectively (Table
or F2CdCH(C6F13), HPO.50 Actually, kinetics of copo-
lymerization of both of these fluorinated monomers led
to the following reactivity ratios:
4
). The SEC chromatograms shown in Figure 8 also
indicate some low molecular weight products tailing in
the range of monomers. The maximum of the SEC traces
shifted toward higher molecular weight with increasing
of fluorine atom in SF5M for the main part of the
copolymer obtained. In the case of experiments III and
IV, the lower molecular weight in the latter is, as
expected, due to the higher concentration of DTBP
initiator (3 mol % vs 1 mol %). However, these measure-
ments cannot be considered quite accurate because of
the lack of standards for VDF polymers. The polydis-
persity index of terpolymers synthesized is in the range
of the statistic distribution (2.0-2.4).
rPFP ) 0.06; rVDF ) 9.0 at 40 °C
rHPO ) 0.9; r VDF ) 12.0 at 75 °C
These values show the low reactivity of the above-
mentioned fluorinated alkenes vs VDF.
1
9
While F NMR spectroscopy shows the insertion of
VDF and HFP base units in the terpolymers, several
methods were used to characterize these fluorinated
terpolymers: the molecular weights by size exclusion
chromatography (SEC with PMMA standards, the poly-
mers were soluble in THF) and the thermal properties
by differential scanning calorimetry (DSC) and ther-
mogravimetric analyses (TGA).
The transfer reaction on the macroradical appears to
be quite negligible on the basis of the small presence of
transfer signals in 19F and H NMR spectra (presence
of triplet of triplets and doublet of multiplets centered
1

Macromolecules, Vol. 38, No. 20, 2005
5
SF -Containing Copolymers 8325
methodology to add SF5Cl to ethylene and VDF, respec-
tively. CF2dCFSF5, (M-III) monomer was synthesized
by radical addition of BrSF5 onto trifluoroethylene
followed by a dehydrobromination. It was found that
M-III monomer does not homopolymerize but copoly-
merizes with VDF by free radical initiation. Its reactiv-
ity with VDF when compared to that of other fluoro-
alkenes (HFP, PMVE, and PPVE) gives the following
decreasing series: HFP > PPVE g PMVE > SF5M; i.e.
the M-III monomer has the lowest reactivity due to the
SF5 bulky side groups.
The terpolymerization of SF5-containing monomers
with vinylidene fluoride (VDF), hexafluoropropene (HFP)
in organic solvent, and peroxyde initiator has been
described for the first time. Indeed, it has been shown
that radical polymerization of SF5M can be successfully
performed in 1,1,1,3,3-pentafluorobutane initiated by di-
tert-butyl peroxide. Interestingly, the terpolymerization
of VDF with HFP and SF5M shows that CH2dCHSF5
monomer was more reactive than CF2dCHSF5 and even
more reactive than CF2dCFSF5.
5
Figure 9. Thermogravimetric curves of VDF/HFP/-SF M
5
terpolymers in air of VDF/HFP/SF terpolymers. Terpolymer
5
compositions of VDF/HFP/SF M in mol %: I, 71.0/11.6/17.4;
II, 83.8/14.1/2.1; III, 78.3/16.4/5.3; IV, 78.1/13.5/8.3.
CH dCH(SF ) > F CdCF(SF ) > F CdCH(SF )
2
5
2
5
2
5
at 6.1 and 5.5 ppm assigned to -CH2CF2H and -CF2-
CF(CF3)H, respectively). On the other hand using the
same strategy of binary poly(VDF-co-SF5MIII) copoly-
mers, the molecular weights of terpolymers can be
assessed by H and F NMR analyses. Equation 6 can
be modified as follows
Both H and 19F NMR analyses enabled the calculation
of molecular weights of binary and ternary SF5M
copolymers.
1
1
19
Finally, DSC, TGA, and GPC analyses indicated that
the terpolymers II and III incorporating SF5 side groups
exhibited better thermal properties and higher molec-
ular weights than terpolymer I. Further work on these
materials, including combustion tests, is in progress.
M ) 64N
+ 150R N
+ R N (MSF M ) + 30
VDF 2 VDF 5 i
n
VDF
1
(9)
where R1 and R2 are the molar ratios of HFP and SF5Mi
monomer units vs VDF, and MSF5Mi stands for the
molecular weights of SF5MI, SF5MII, and SF5MIII
monomers, respectively. The results obtained are shown
in Table 3 and compared to SEC molecular weights.
They follow the same tendency, but they have higher
values than SEC as discussed before.
Thermogravimetry curves (Figure 9) show that these
terpolymers exhibit a good thermal stability since their
decomposition started from 170 to 250 °C, for poly(VDF-
ter-HFP-ter-SF5M) terpolymers. For example, terpoly-
mer I (curve I) is the least thermally stable because of
the entirely hydrogenated vinyl group in M-I and also
because of its low molecular weight (hence inducing a
certain evaporation of the terpolymer before its degra-
dation). The higher the fluorine content, the higher
thermostability of the obtained terpolymer.
Acknowledgment. The authors thank the Solvay
S. A. (Tavaux and Brussels in France and Belgium,
respectively) for the generous gifts of vinylidene fluoride,
hexafluoropropene, and 1,1,1,3,3-pentafluorobutane.
Supporting Information Available: NMR and FT-IR
spectra and DSC curves of poly(VDF-Co-MIII) copolymers and
poly(VDF-ter-HFP-ter-SF M ) terpolymers. This material is
5 i
available free of charge via the Internet at http://pubs.acs.org.
References and Notes
(
1) (a) Feiring, A. E. Fluoroplastics. In Banks, R. E., Smart, B.
E., Tatlow, J. C. Ed. Organofluorine Chemistry: Principles
and Commercial Applications; Plenum Press: New York,
1994; Vol. 15, pp 339-372. (b) Scheirs, J. Modern Fluoropoly-
mers; Wiley: New York, 1997. (c) Hougham, G.; Davidson,
T.; Cassidy, P.; Johns, K. Fluoropolymers; Kluvert: New
York, 1999. (d) Ameduri, B.; Boutevin, B. Well-Architectured
Fluoropolymers: Synthesis, Properties and Applications; Elsevi-
er: Amsterdam, 2004.
The glass transition temperatures (Tg) of the different
fluorinated terpolymers were assessed by differential
scanning calorimetry (DSC), and the results are listed
in Table 4. In the poly(VDF-ter-HFP-ter-SF5M) terpoly-
mers, Tg values were ranging from -40 to -50 °C
without any other transitions, showing amorphous
behavior. With such Tg values, and as reported in the
(
(
2) Banks, B. A. The use of Fluoropolymers in Space Applica-
tions. In Modern Fluoropolymers; Scheirs, J., Ed.; Wiley and
Sons: New York, 1999; Chapter 4, pp 103-114.
3) a) Kobayashi, T.; Munekuta, S.; Unoki, E. European Patent
239,935, 1987. (b)Yamamoto, S.; Matsumoto, M.; Shimada,
T. European Patent 256,765, 1988. (c) Skutnik, K. AU Patent
569,145, 1988.
8
,9a
literature,
it is known that fluoropolymers, contain-
(
4) Boutevin, B.; Pietrasanta, Y. Les Acrylates et poly Acrylates
fluor e´ s; Erec: Paris, 1998.
ing VDF and HFP base units only, exhibit an average
Tg of -26 °C and are fluoroelastomers.
(5) Brady, R. Chem. Br. 1990, 26 (5), 427-438.
Finally, regarding the results gathered in Table 4, it
appears that the hydrogenated monomer M-I is more
reactive than M-II and M-III monomers containing two
and three F- atoms in the vinyl group, respectively.
(6) (a) Tournut, C. Macromol. Symp. 1994, 82, 99-109. (b)
Tournut, C. J. Thermoplastic Copolymers of Vinylidene
Fluoride. In Modern Fluoropolymers; Scheirs, J., Ed.; Wiley:
New York, 1997; Chapter 31, pp 577-596.
(
7) (a) Cook, D.; Lynn, M. Rapra Rev. Rep. 1995, 3, Report 32,
Shrewbury, pp 1-27. (b) Logothetis A. L. Prog. Polym. Sci.
1989, 14, 251-285. (c) Van Cleef, A. Fluoroelastomers. In
Modern Fluoropolymers; Scheirs, J., Ed.; Wiley: New York,
Conclusion
Monomers CH2dCHSF5 (M-I) and CF2dCHSF5 (M-
II) were prepared by using a new Et3B initiation
1
997; Chapter 32, pp 597-614. (d) Ameduri, B.; Boutevin,
B.; Kostov, G. Prog. Polym. Sci. 2001, 26, 105-187.

8326 Kostov et al.
Macromolecules, Vol. 38, No. 20, 2005
(
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