Synthesis and characterization of novel alternating fluorinated copolymers bearing oligo(ethylene oxide) side chains

Article abstract of DOI:10.1002/pola.26463

The synthesis and characterization of novel poly(CTFE-g-oligoEO) graft copolymers [chlorotrifluoroethylene (CTFE) and ethylene oxide (EO)] are presented. First, vinyl ether monomers bearing oligo(EO) were prepared by transetherification of ω-hydroxyoligo(EO) with ethyl vinyl ether catalyzed by a palladium complex in 70-84% yields. Two vinyl ethers of different molecular weights (three and 10 EO units) were thus obtained. Then, radical copolymerization of the above vinyl ethers with CTFE led to alternating poly(CTFE-alt-VE) copolymers that bore oligo(OE) side chains in satisfactory yields (65%). These original poly(CTFE-g-oligoEO) graft copolymers were characterized by ¹H, ¹⁹F, and ¹³C NMR spectroscopy. Their molecular weights reached 19,000 g mol^-1, and their thermal properties were investigated while their glass transition temperatures ranged between -42 and -36 °C. Their thermogravimetric analyses under air showed decomposition temperatures of 270 °C with 10% weight loss (T_d,10%). These novel copolymers are of potential interest as polymer electrolytes in lithium ion batteries, showing room temperature conductivities ranging from 4.49 × 10^-7 to 1.45 × 10^-6 S cm^-1 for unplasticized material.

Full text of DOI:10.1002/pola.26463

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Synthesis and Characterization of Novel Alternating Fluorinated
Copolymers Bearing Oligo(ethylene oxide) Side Chains
1
2
1
2
1
ꢀ ꢀ
Ali Alaaeddine, Andrew Hess, Frederic Boschet, Harry Allcock, Bruno Ameduri
1
ꢀ
ꢀ
ꢀ
Institut Charles Gerhardt, Ingenierie et Architectures Macromoleculaires, UMR CNRS 5253, Ecole Nationale Superieure de
Chimie de Montpellier, 8 Rue de l’Ecole Normale, 34296 Montpellier, France
2Pennsylvania State University, Chemistry Department, University Park, Pennsylvania 1680
Correspondence to: B. Ameduri (E-mail: ameduri@enscm.fr)
Received 28 September 2012; accepted 25 October 2012; published online 5 December 2012
DOI: 10.1002/pola.26463
ABSTRACT: The synthesis and characterization of novel poly
(CTFE-g-oligoEO) graft copolymers [chlorotrifluoroethylene
(CTFE) and ethylene oxide (EO)] are presented. First, vinyl
ether monomers bearing oligo(EO) were prepared by transe-
therification of x-hydroxyoligo(EO) with ethyl vinyl ether
catalyzed by a palladium complex in 70–84% yields. Two vinyl
ethers of different molecular weights (three and 10 EO units)
were thus obtained. Then, radical copolymerization of the
above vinyl ethers with CTFE led to alternating poly(CTFE-alt-
VE) copolymers that bore oligo(OE) side chains in satisfactory
yields (65%). These original poly(CTFE-g-oligoEO) graft
copolymers were characterized by 1H, 19F, and 13C NMR spec-
glass transition temperatures ranged between ꢀ42 and ꢀ36
ꢁC. Their thermogravimetric analyses under air showed
decomposition temperatures of 270 ꢁC with 10% weight loss
(Td,10%). These novel copolymers are of potential interest as
polymer electrolytes in lithium ion batteries, showing room
temperature conductivities ranging from 4.49
ꢂ
10ꢀ7 to
1.45 ꢂ 10ꢀ6 S cmꢀ1 for unplasticized material.
2012 Wiley
C
V
Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51,
977–986
KEYWORDS: chlorotrifluoroethylene; fluoropolymer; macromo-
nomers; nuclear magnetic resonance; polyethers; poly(ethylene
oxide); radical copolymerization; thermal properties; vinyl
ethers
troscopy. Their molecular weights reached 19,000 g molꢀ1
,
and their thermal properties were investigated while their
INTRODUCTION Fluoropolymers exhibit remarkable proper-
ties,1–5 such as chemical resistance (to acids, bases, and
organic solvents), thermostability, low dielectric constants
and dissipation factors, hydrophobic and oleophobic proper-
ties, excellent weathering, and interesting surface properties.
Hence, these high added value materials have found specific
applications in many fields of high technology (aerospace,
aeronautics, automotive, and electronic industries). Most flu-
orinated (co)polymers are synthesized by radical (co)poly-
merization. Actually alternating copolymers are scarce,
except E-TFE, E-CTFE, and poly(VDF-alt-HFiB) copolymers
[ethylene (E), tetrafluoroethylene (TFE), chlorotrifluoroethy-
lene (CTFE), vinylidene fluoride (VDF), and hexafluoroisobu-
tylene (HFiB)]. To our knowledge, creating hydrophilic
fluoropolymers is a challenge,6–8 and it was of interest
to synthesize novel fluorinated (co)polymers bearing oligo
(ethylene oxide) grafts.
batteries, especially with plasticizers. PEO is capable of com-
plexing the lithium salts and facilitating the transport of Liþ
cations while maintaining an excellent interfacial stability.
Among these polymer electrolytes, fluorinated polymers
based on PEO are an attractive option since the fluorinated
units introduce properties such as thermostability, chemical
stability, and desirable mechanical properties. Several
authors have prepared blends of poly(vinylidene fluoride)
(PVDF) with PEO20 or PEO-b-PMMA21 diblock copolymers
[poly(methyl methacrylate) (PMMA)] in the presence of
dibutyl phthalates in 7/3/10 w/w proportions.
Cui et al.22 reported blends of PEO with other homopoly-
mers or copolymers based on PEO and poly(propylene
oxide) (PPO). (Semi-)Interpenetrated networks prepared by
photopolymerization of blends of PVDF with dimethacrylate
derivatives containing PEO units have shown promising
conductivity values (1.5 ꢂ 10ꢀ3 S cmꢀ1).23,24 Other authors
prepared some PVDF-g-PEO graft copolymers from PVDF
activated by ozone, c-ray, or 60Co irradiation.25 Chen et al.26
prepared a novel PVDF-g-PMMA graft copolymer that was
further chemically changed by transesterification with
The development of new electrolytes endowed with good
thermostability is still a major breakthrough.9–12 Electrolytes
based on poly(ethylene oxide) (PEO) derivatives or ana-
logs13–19 have good conducting properties for lithium ion
C
V
2012 Wiley Periodicals, Inc.
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EXPERIMENTAL
PEO-OH leading to PVDF-g-PEOM [PEO-methacrylate
(PEOM)]. Furthermore, a team from MIT27 achieved the same
graft copolymer by atom transfer polymerization (ATRP) of
PEOM (Mn ¼ 475 g molꢀ1) using PVDF as the macroinitiator
in the presence of CuCl complexed by N,N,N0,N00,N00-pentame-
thyldiethylene triamine. The same approach was reported by
a Korean team28 but from poly(VDF-co-CTFE) copolymer
(CTFE) using a direct initiation on the CACl bonds to yield
poly(VDF-co-CTFE)-g-PEOM graft copolymers. The major
drawback of the ATRP method is the difficulty in eliminating
all copper ions, which can inhibit the transport of lithium ions
resulting in lower battery performances.
Materials
Tert-butylperoxypivalate (TBPPI) was provided by Akzo
Nobel (Compie`gne, France). CTFE, PCTFE (for Fig. 5), and
1,1,1,3,3-pentafluorobutane (C4F5H5) were provided by
Honeywell and Solvay S.A. (Tavaux, France and Bruxelles,
Belgium) and were used as received. Ethyl vinyl ether, palla-
dium acetate, triethylene glycol monomethyl ether, poly
(ethylene glycol) monomethyl ether (DPn ¼ 10), 1,10-
phenanthroline, sodium sulfate (Na2SO4), potassium carbon-
ate (K2CO3), acetone (analytical grade), dichloromethane
(DCM, analytical grade), methanol (analytical grade), and tet-
rahydrofuran (THF, analytical grade) were purchased from
Sigma-Aldrich (Saint Quentin-Fallavier, France). Deuterated
solvents for NMR spectroscopy were purchased from
Euroiso-top (Grenoble, France) (purity > 99.8%). Lithium
trifluoromethanesulfonate (triflate) was purchased from
Sigma-Aldrich (Milwaukee).
Although there are numerous reports on the synthesis and
use of PVDF-g-PEO graft copolymers, to the best of our
knowledge, there is only one patent that disclosed the prepa-
ration of fluorinated copolymers based on CTFE bearing PEO
side-chains.29 Actually, such PCTFE-g-PEO graft copolymers
are of interest since they exhibit good thermal properties,
good chemical inertness, and are stable at low and high elec-
trochemical potentials, thus fulfilling the requirements for
Li-ion battery electrolytes.
Characterization
Nuclear Magnetic Resonance
The nuclear magnetic resonance (NMR) spectra were
recorded on a Bruker AC 400 instrument, using deuterated
chloroform, d6-N,N-dimethylsulfoxide, and d6-acetone as the
solvents and tetramethylsilane (TMS) (or CFCl3) as the refer-
We chose CTFE30 as the fluoroolefin because it is an elec-
tron–acceptor monomer that is known to yield alternating
copolymers with vinyl ethers via an ‘‘acceptor–donor’’
copolymerization.4,31 This peculiarity arises from the elec-
tron-accepting character of the fluorinated olefins (CTFE:
e ¼ 1.56)32,33, and the electron-donating character of the
vinyl ether (ꢀ2.0 < e < ꢀ1.5).34–36 Furthermore, vinyl
ethers do not homopolymerize by radical polymerization.37,38
The poly(CTFE-alt-VE) copolymers39–57 exhibit interesting
properties arising from the 50 mol % of fluorinated units3,4
(thermostability, film-forming, hydrophobicity, oleophobicity,
chemical inertness, mechanical properties, and electrochemi-
cal stability) and the other 50 mol % of the vinyl ether
brings the complementary properties (solubility, crosslinking,
hydrophilicity, softness, adhesion to metal, and affinity with
the lithium anions).31,35,36,49,50,57 Thus, these are copolymers
endowed with good thermal and chemical stability and with
excellent mechanical properties.
1
ences for H (or 19F) nuclei. Coupling constants and chemical
shifts are given in hertz (Hz) and part per million (ppm),
respectively. The experimental conditions for recording 1H,
19
13C, (or F) NMR spectra were as follows: flip angle 90ꢁ (or
30ꢁ), acquisition time 4.5 s (or 0.7 s), pulse delay 2 s (or 2
s), number of scans 128 (or 512), and a pulse width of 5 ms
for 19F NMR.
Size Exclusion Chromatography
Size exclusion chromatograms (SEC) were recorded using a
GPC 50 from Polymer Labs (Now Varian) with its corre-
sponding software (Cirrus). The system used 2 PL Gel Mixed
C columns (200 < Mw < 20,000,000 g molꢀ1) with tetrahy-
drofuran as the eluent with a flow rate of 1.0 mL minꢀ1 at
room temperature. Both RI and UV detectors can be
used. Polystyrene standards were used for the calibration.
Sample concentration was 1 wt %. Analyses were achieved
by injection of 20 mL of 20 mm filtered polymer solution
(5 mg mLꢀ1).
Several authors have reported the radical copolymerization
of vinyl ethers that bear PEO chains (H2C¼¼CHAO-PEO)58–61
but none of them have been used conjointly with a fluori-
nated olefin to prepare either oligomers or copolymers
having
a fluorinated backbone and PEO side chains
Thermogravimetric analyses
(especially those of CTFE31).
Thermogravimetric analyses (TGA) were performed with a
TGA Q50 apparatus from TA Instruments, under air, at a
The objective of this work concerns the synthesis of novel
fluorinated copolymers obtained by radical copolymerization
of commercially available fluoroolefin (CTFE) with vinyl
ether macromonomers bearing oligo(EO) side chains. Such
vinyl ethers were obtained by transetherification of ethyl
vinyl ether with oligo(ethylene glycol) monomethyl ether (n
¼ 3 or 10) catalyzed by a palladium(II) complex. Such mac-
romonomers with different molecular weights (PEO of 300
or 500 g molꢀ1) were prepared leading to copolymers with
different morphologies, glass transition temperatures, and
melting temperatures.
ꢀ1
ꢁ
heating rate of 10 C min from room temperature up to a
maximum of 550 ꢁC. The sample weight varied between 10
and 15 mg.
Differential Scanning Calorimetry
Differential scanning calorimetry (DSC) analyses were car-
ried out with a Netzsch 200F3 DSC apparatus equipped with
Proteus soꢁftware under nitrogen atmosphere at a heating
rate of 20 C minꢀ1. The temperature range was from ꢀ100
to þ200 ꢁC. The DSC system was first calibrated using in-
dium and n-hexane standards. The second run led to the Tg
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values assessed from the inflection point in the heat capacity
jump. The sample weight was about 10 mg.
times with 100 mL of dichloromethane. The organic phase
was dried with sodium sulfate, filtered, and the dichlorome-
thane evaporated. The final product is a yellow liquid
obtained in 84% yield.
Elemental analyses
Weight percentages of carbon, fluorine, chlorine, and hydro-
gen atoms were assessed by elemental analysis (EA) at the
CNRS, Service Central d’Analyse (Solaize, France) on a CH
elemental analyzer equipped with a CO2/H2O infrared detec-
tor. Polymer compositions were calculated using equations:
Synthesis of Methoxypoly(ethylene oxide) Vinyl Ether
(PEOVE10)
The experimental procedure and purification were similar as
that of methoxy-tri(ethylene oxide) vinyl ether PEOVE3. Pal-
ladium acetate (448 mg, 2.0 mmol), dichloromethane (25
mL), 1,10-phenanthroline (540 mg, 3.0 mmol), poly(ethylene
glycol) monomethyl ether, (20.00 g, 0.04 mol), and ethyl
vinyl ether (17.3 g, 0.24 mol) were introduced in the auto-
clave. The reaction was carried out at 60 ꢁC for 24 h. The
purification procedure was similar to that used above for
PEOVE3. The final product was a yellow liquid obtained in
71% yield.
%H
ð6 þ 4nÞq
%C 24p þ ð36 þ 24nÞq
%F 57p
¼
¼
%C 24p þ ð36 þ 24nÞq
p þ q ¼ 1
where p, q, and n are the percentages of fluoroolefin, of vinyl
ether, and number of ethyleneoxy groups in PEO (n ¼ 3 or
10), respectively.
Radical Copolymerization of Chlorotrifluoroethylene with
Vinyl Ethers
The radical copolymerizations were performed in a 160-mL
Hastelloy Parr autoclave system (HC 276) equipped with a
manometer, a mechanical Hastelloy anchor, a rupture disk
(3000 PSI), inlet and outlet valves. An electronic device regu-
lated and controlled both the stirring and heating of the
autoclave. Before reaction, the autoclave was pressurized
with 30 bars of nitrogen to check for leaks. The autoclave
was then conditioned for the reaction with vacuum (10ꢀ2
mbar) for 40 min to remove any trace of oxygen. The liquids
and dissolved solids were introduced via a funnel and then
the gas (CTFE) was introduced by double weighing (i.e., the
difference of weight before and after filling the autoclave
with the gas).
Conductivity Assessments
Before conductivity assessment, each polymer was further
purified by dialysis versus THF (3 days) followed by dialysis
versus dichloromethane (DCM) (3 days) using Spectra/Por
regenerated cellulose membranes with a molecular weight
cutoff of 1000. Ionic conductivity was measured by electro-
chemical impedance spectroscopy using a Solartron 1260 im-
pedance analyzer and a custom-built two electrode-cell with
platinum electrodes. The temperature of each sample was
controlled during analysis by a temperature-regulated oven.
Each reported value is the average of five measurements.
Electrolyte samples were prepared by dissolving both the
polymer and lithium triflate in acetone. The acetone was
then evaporated, and each sample was thoroughly dried by
lyophilization. The ratio of lithium triflate to polymer was
held constant at 0.235 lithium ions per repeating unit of
polymer. An additional sample of poly(CTFE-alt-PEOVE10)
was prepared to contain the same ratio of oxygen atoms to
lithium ions as the sample of poly(CTFE-alt-PEOVE3) with
0.235 Liþ per repeating unit (17.0 O/Liþ). Control samples
consisted of the pure polymer without any lithium triflate.
Copolymerization of PEOVE3 with chlorotrifluoroethylene
To prevent any homopolymerization of the vinyl ether by
acid catalysis (i.e., cationic initiation) and the formation of
the acetal from the vinyl ether, potassium carbonate (161
mg, 1.16 mmol) was introduced in the reaction prior to con-
ditioning. PEOVE3 (7.30 g, 0.0338 mol), tert-butyl peroxypi-
valate (TBPPi; 1.80 g, 7.76 mmol), and 50 mL of 1,1,1,3,3-
pentafluorobutane were inserted via a tight funnel. CTFE
(13.5 g, 0.116 mol) was then introduced by double weighing.
The copolymerization was carried out at 74 ꢁC for 15 h.
First, an increase of pressure was noted due to the exother-
micity of this reaction. Then, a pressure drop was observed
correlated to the consumption of the CTFE during the poly-
merization. After the polymerization, the reactor was cooled
in an ice bath for 30 min and then degassed. No gas was
released meaning a high gas conversion (though CTFE has a
good solubility in the 1,1,1,3,3-pentafluorobutane). The reac-
tion mixture was dissolved in acetone and then precipitated
from pentane to eliminate any residual solvent, monomer,
potassium carbonate, initiator, and oligomers. The product
was dried under vacuum at 50 ꢁC until constant weight
yielding 12.6 g of a red gum (5) (yield ¼ 61%).
Synthesis
Synthesis of Methoxy-tri(ethylene oxide) Vinyl Ether
(PEOVE3)
In a Schlenk flask under inert atmosphere, palladium acetate
(380 mg, 1.69 mmol) was dissolved in DCM (10 mL). A solu-
tion of 1,10-phenanthroline (458 mg, 2.54 mmol) in DCM
(10 mL) was then added into the Schlenk. The reaction me-
dium was further stirred at room temperature for 30 min to
generate the palladium catalyst in situ. A triethylene glycol
monomethyl ether solution (13.90 g, 0.0847 mol) and ethyl
vinyl ether (36.66 g, 0.50 mol) were added to the reaction
medium, which was then transferred into an autoclave and
heated at 60 ꢁC for 24 h. After cooling, the autoclave was
opened and both DCM and ethyl vinyl ether were evaporated
under vacuum. The remaining product was dissolved in 100
mL of deionized water. The mixture was extracted three
Copolymerization of PEOVE10 with Chlorotrifluoroethylene
The experimental procedure was similar as that of the radi-
cal copolymerization of CTFE with vinyl ether PEOVE3.
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SCHEME 1 Preparation of vinyl ethers bearing oligo(ethylene oxide) (PEO) chains (PEOVE (n ¼ 3 or 10) and their radical copoly-
merization with chlorotrifluoroethylene (CTFE).
ꢁ
Potassium carbonate (138 mg, 1 mmol), PEOVE10 (20.41 g,
0.0388 mol), TBPPi (1.80 g, 7.76 mmol), 50 mL of 1,1,1,3,3-
pentafluorobutane, and CTFE (13.5 g, 0.116 mol) were intro-
duced in the autoclave. The copolymerization was carried
phenanthroline (as the ligand) at 60 C. Using these optimized
parameters,49,50 PEOVE3 and PEOVE10 monomers were pre-
pared by transetherification of ethyl vinyl ether and PEOMe
(Scheme 1). The reaction was carried out in the presence of
ꢁ
ꢁ
out at 74 C for 15 h. Similar increase and drop of pressure
dichloromethane at 60 C in an autoclave yielding both mac-
were observed. Similar postcopolymerization procedure,
work-up, and purification were also carried out. The copoly-
merization yielded 15.1 g of a red gum after precipitation
(6) (yield ¼ 68%).
romonomers in 84 and 71 mol % yield, respectively.
PEOVEn (n ¼ 3 or 10) macromonomers were characterized
1
1
by H and 13C NMꢁR spectroscopy. Both H NMR spectra (Fig.
1) in CDCl3 at 20 C displays the two nonequivalent protons
CHaHb of the vinyl group as two doublets of doublets at 4.11
and 3.93 ppm for PEOVE3 and PEOVE10. The doublet of
doublets assigned to the terminal methyne proton (¼¼CHA)
of the vinyl ether is located at 6.41 ppm. The same observa-
tion can be noted for the methylene group of the PEO (d ¼
3.70 ppm). The singlet assigned to the methoxy group of
PEOMe is located at 3.30 ppm for PEOVE3 and PEOVE10.
RESULTS AND DISCUSSION
The synthesis of the PEO-bearing vinyl ether (PEOVEn,
where n corresponds to the number of ethylene oxide units
in the PEO chain) and their radical copolymerization with
CTFE were carried out according to Scheme 1.
Preparation of the Macromonomer
Our goal was to prepare liquid vinyl ether monomers bear-
ing PEO chain from poly(ethylene glycol) monomethyl ether
(PEGMe) (Scheme 1). Four main synthetic pathways have
been reported for the chemical modification of an alcohol
with a functional vinyl ether: addition onto acetylene,62
phase transfer catalysis based on a Williamson reaction
(between an alcoholate and 2-chloroethyl vinyl ether),63–65
the modification of vinyl acetate in the presence of an irid-
ium complex,66 and transetherification.63,67–72 This latter
strategy has been extensively studied in the presence of
either mercuric acetate or palladium acetate, especially by
Watanabe and Conlon,67 Mc Keon,73 and Boutevin and Yous-
sef.63 This last study even compared the transetherification
with the Williamson reaction. More recently, Pichavant74
reported the synthesis of a vinyl ether by transetherification
catalyzed by a palladium (II) complex in the presence of
ethyl vinyl ether in dichloromethane.
Radical Copolymerization of PEOVEn with
Chlorotrifluoroethylene
The radical copolymerizations were carried out in an auto-
clave, in the presence of tert-butylperoxypivalate (TBPPi 5
mol % compared to monomers) and 1,1,1,3,3-pentafluorobu-
tane at 74 ꢁC, as the initiator and solvent, respectively
(Scheme 1). The amount of initiator (5 mol %) may be con-
sidered high compared to the usual conditions (< 1 mol %),
but for the intended use (polymer electrolyte for lithium bat-
teries) low-molecular-weight polymers are highly desirable,
and thus a high quantity of initiator was required.
A small amount of potassium carbonate (K2CO3) was added
into the polymerization media to prevent from both the cati-
onic homopolymerization and the formation of acetal from
vinyl ether.75 CTFE was used in slight excess to enable the
complete consumption of the vinyl ether.
Recently, we synthesized novel vinyl ethers bearing lateral
chloromethyl49 or carbonate groups50,57 by transetherifica-
tion catalyzed by a palladium (II) complex generated in situ.
Reactions were carried out in dichloromethane in the
presence of 2% of palladium (II) acetate catalyst and 1,10
The radical copolymerization of CTFE with vinyl ether is an
exothermic reaction, and a rapid increase of pressure in the
autoclave was observed (12 bar), followed by a sharp drop
of pressure (3 bar). Such a copolymerization is called
‘‘acceptor–donor copolymerization’’ and yields alternating
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FIGURE 1 1H NMR spectra of PEOVE3 (lower spectrum) and PEOVE10 (upper spectrum) recorded in CDCl3 at room temperature.
copolymers. Poly(CTFE-alt-PEOVEn) copolymers were
obtained and their characteristics are listed in Table 1.
indices for such a copolymerization (1.70 < Mw/Mn < 2.48).
1H NMR spectra (Fig. 2) of poly(CTFE-alt-PEOVEx) exhibit
the absence of signals centered at 6.41 ppm characteristic of
unreacted VE vinylic protons. However, their polymerized
equivalent ACH2ACH(PEOMe)A can be found between 2.5
and 3.0 ppm, and between 4.5 and 5.0 ppm for the methyl-
ene and methyne protons, respectively. Both signals are com-
plete and spread due to the presence of two types of asym-
metric carbons leading to two diastereoisomers, which
makes these protons nonequivalent (anisochronous). Methyl-
enic protons of the PEO chain (AOCH2A) are similar in both
polymers and are located at 3.65 ppm, while the protons ad-
jacent to the oxygen from the vinyl ether are located at 3.93
ppm. However, the methoxy protons can be found at about
3.30 ppm.
When using t-butylperoxypivalateꢁ (5 mol % with respect to
monomers) as the initiator at 75 C, the yield of polymeriza-
tion after precipitation ranged between 61 and 68%. This is
a satisfactory value compared to those of the literature for
the radical copolymerization of CTFE with VE in solution
that ranges between 47 and 88%.31,35,36 The obtained
copolymers were isolated by precipitation from pentane
yielding red to brown very viscous liquids soluble in polar
solvents (acetone, DMF, DMSO, and THF), while PCTFE was
not soluble in such solvents. Both copolymers were charac-
1
terized by H, 19F, and 13C NMR spectroscopy, size exclusion
chromatography (SEC) and elemental analysis. SEC showed
that the molar masses of the poly(CTFE-alt-PEOVE)
copolymers ranged from 13,700 to 19,000 g molꢀ1 (com-
pared to PS standards) and present typical polydispersity
Furthermore, the 19F NMR spectra of the poly(CTFE-alt-PEOVE)
copolymers (Fig. 3) do not exhibit the characteristic signal at
TABLE 1 Radical Copolymerization of PEOVE3 and PEOVE10 with Chlorotrifluoroethylene (CTFE)
Copolymer
Composition (%)b
Monomer Feed Ratio (%)a
c
Mn,exp
c
Entries
CTFE
PEOVE
Yield (%)
CTFE
PEOVE
(g molꢀ1
)
Mw/Mn
1
2
a
65
65
PEOVE3 (35)
PEOVE10 (35)
61
68
53
49
47
51
13,700
19,000
2.4
1.7
b
c
Polymerization conditions: t-butylperoxypivalate (5 mol %), Solvent:
1,1,1,3,3-pentafluorobutane, potassium carbonate (3 mol %), T ¼ 74 ꢁC
for 14 h. Products characterized after precipitation in pentane.
Copolymer composition was assessed from elemental analyses.
Molar masses and polydispersity assessed from SEC calibrated with
polystyrene standards.
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FIGURE 2 1H NMR spectra of poly(CTFE-alt-PEOVE3) (lower spectrum) and poly(CTFE-alt-PEOVE10) (upper spectrum) recorded in
acetone-d6 at room temperature.
ꢀ127 ppm of the CTFE-CTFE dyads, that is, the central CFCl in
ACF2CFClACF2CFClA.52,57,76 This is evidence that these copoly-
mers have an alternating A [CF2CFClACH2CH(OAPEGMe)]nA
structure. However, these spectra showed that the chemical
shifts assigned to the CTFE units are independent of the PEOMe
chain length. Signals ranging between ꢀ107.0 and ꢀ123.1
ppm,53 and the signal centered at ꢀ124.4 ppm were assigned
to the ACF2A and ACFClA of both A and B diastereoisomers,
respectively, as depicted in Figure 3.
Unlike other poly(fluoroalkene-co-vinyl ether) copolymers,31
these new poly(CTFE-alt-PEOVE) copolymers were also
characterized by DEPT 13C NMR spectroscopy (Fig. 4). The
spectra show that all the signals assigned to the carbons
FIGURE 3 19F NMR spectrum of poly(CTFE-alt-PEOVE3) recorded in acetone-d6 at room temperature.
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FIGURE 4 13C NMR spectra of poly(CTFE-alt-PEOVE3) (lower spectrum) and poly(CTFE-alt-PEOVE10) (upper spectrum) recorded in
acetone-d6 at room temperature.
from either CTFE or the vinyl ether and are not much
affected by the PEOMe chain length (3 or 10 units). Several
signals assigned to the CTFE units were observed at 121.05,
118.57, 115.94, 113.81, 111.80, and 109.97 ppm (n ¼ 3) or,
121.04, 118.31, 115.42, 113.60, 111.40, and 109.40 (x ¼
10). The signals assigned to the methylene in the
ACH2ACH(PEOMe)A group of the vinyl ether units are
located at 38.93 (n ¼ 3) or 39.18 ppm (n ¼ 10). The
two signals either at 78.73 and 75.75 ppm (n ¼ 3) or 78.56
and 75.75 (n ¼ 10) resulting from both diastereoisomers
were assigned to the asymmetric carbon atom in
ACH2AC*H(PEGMe)A. These tertiary carbon atoms induced
negative signals in DEPT 13C NMR spectra. The AOACH2A
adjacent to the backbone and the methoxy carbon (AOCH3)
are located at 72.41 and 58.79 ppm, or 72.81 and 58.94
ppm for copolymers having n ¼ 3 and 10, respectively. The
carbon atoms of the PEOMe chains are located between
70.41 and 74.07, or 69.90 and 73.62 ppm for n ¼ 3 and 10,
respectively.
mers: poly(CTFE-alt-PEOVE3) degradation initiated at about
215 ꢁC while that ꢁ of poly(CTFE-alt-PEOVE10) copolymer
ꢁ
started from at 267 C and lasted up to 540 C in both cases.
This difference was attributed to the increased thermostabil-
ity with increasing PEO chain length. Though PCTFE displays
a very high thermostability, that of both these copolymers
can be regarded as fair to satisfactory as explained by the
good chemical and thermal stability of the CTFE units (the
degradation of which begins at about 300 ꢁC) compensating
for the poor thermal stability of the VE units (that usually
occurs as soon as 150 ꢁC).77,78 A more detailed analysis of
the TGA thermograms provides evidence of two main decom-
positions: Although the TGA experiments did not clearly
evaluate the durability of these polymers at a given tempera-
ture, we can consider that in the operating temperature
range for the lithium-ion batteries (ꢀ30 to þ150 ꢁC), these
polymers should not degrade.
Such a huge difference with the thermostability of PCTFE
may also confirm the alternated character of these copoly-
mers. DSC analyses (Table 2) of the poly(CTFE-alt-PEOVEx)
copolymers demonstrate both the decrease of the glass tran-
sition temperature with increasing PEO content (i.e., chain
length) and the absence of melting temperature due to the
amorphous character of these copolymers.79,80 Actually, the
presence of the ether groups in PEO induces lower Tg. The
Thermal properties of these copolymers were assessed by
TGA and DSC. Figure 5 represents the TGA thermograms for
both poly(CTFE-alt-PEOVE3) and poly(CTFE-alt-PEOVE10)
copolymers, and PCTFE under air. Only one main degrada-
tion was observed and the decomposition temperatures at 5
and 10 percent weight loss were different in both copoly-
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FIGURE 5 TGA thermograms obtained under air at 10 ꢁC minꢀ1 for both poly(CTFE-alt-PEOVEx) copolymers (n ¼ 3 and 10) and
PCTFE (dotted line).
thermal propertiesꢁ of these copolymers contrast with the
of PCTFE,30 which is a semicrystalline homopolymer. These
ature conductivity of PEO homopolymer, 1.3 ꢂ 10ꢀ6 S cmꢀ1
,
ꢁ
high Tg (ca. 55–70 C) and melting point (Tm ¼ 214–220 C)
measured at an optimized lithium content of one lithium ion
per 24 r.u.81 The room temperature (30 C) results are sum-
ꢁ
alternating poly(CTFE-al-VE) copolymers do not contain any
marized in Table 3. When the electrolytes are compared
using equal ratios of Liþ per repeating unit, one might
expect the electrolyte containing the longer PEO chains to
have a higher conductivity. However, the conductivity is
actually lower because the concentration of lithium ions is
lower due to the added volume of the longer PEO chains.
oligo(CTFE)
sequences
that
would
allow
any
crystallization.30
These fluorinated elastomers have remarkable properties
(good thermostability, low glass transition temperature, and
amorphous character) fulfilling the requirements for polymer
electrolytes in lithium-ion batteries.
An additional electrolyte sample containing the same ratio of
oxygen atoms to Liþ as the previous electrolyte based on
poly(CTFE-alt-PEOVE3) (17.0 O/Liþ) was prepared from
poly(CTFE-alt-PEOVE10). When the conductivity of the
Conductivities of these Copolymers
Electrolyte samples were prepared using each of the copoly-
mers by dissolving them in acetone along with lithium tri-
flate. The amount of lithium in each sample was held con-
stant at a ratio of 0.235 lithium ions per repeating unit (r.u.)
of polymer. Ionic conductivity was measured as a function of
temperature by electrochemical impedanceꢁanalysis. Even at
ꢁ
30 C, both copolymers are more than 60 C above their Tg,
and therefore, the electrolytes exhibit Arrhenius-type behav-
ior (Fig. 6) in the temperature range studied (from 30 to
110 ꢁC). The electrolyte prepared from poly(CTFE-alt-
PEOVE3) copolymer showed the best room temperature
conductivity of 1.45 ꢂ 10ꢀ6 S cmꢀ1, while the electrolyte
prepared from poly(CTFE-alt-PEOVE10) cooligomer had a
slightly lower room temperature conductivity of 8.92 ꢂ 10ꢀ7
S cmꢀ1. These conductivities are similar to the room temper-
TABLE 2 Glass Transition (Tg) and Decomposition
Temperatures (Td) of Poly(CTFE-alt-PEOVEn) Copolymers
Obtained by DSC and TGA under Air, Respectively
FIGURE 6 Arrhenius plots of the conductivity of poly(CTFE-alt-
PEOVEn) copolymers-based electrolytes. Circles mark the
electrolyte containing an equal Liþ/repeating unit (r.u.) ratio,
whereas triangles represent the electrolyte containing an equal
O/Liþ ratio. Each point represents the average of five measure-
ments. All points have an error of less than 1.5%.
(Co)polymers
Tg (ꢁC)
Td,5% (ꢁC)
Td,10% (ꢁC)
poly(CTFE-alt-PEOVE3)
poly(CTFE-alt-PEOVE10)
PCTFE
ꢀ36
160
247
420
215
269
435
ꢀ42
55–70
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TABLE 3 Conductivity Values of Poly(CTFE-alt-PEOVEn)
Copolymer Electrolytes at 30 8C
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