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Journal of the Taiwan Institute of Chemical Engineers


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Recent advances in the controlled radical (co) polymerization of


uoroalkenes and applications therefrom
Bruno Ameduri *
Engineering and Macromolecular Architectures, Institut Charles Gerhardt UMR (CNRS), 5253 Ecole Nationale Superieure de Chimie de Montpellier, 8 Rue Ecole
Normale, 34296 Montpellier Cedex 5, France

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 14 February 2014
Received in revised form 5 May 2014
Accepted 11 May 2014
Available online xxx

Since late 1970s, extensive studies on controlled (or pseudoliving) radical polymerizations (CRP) have
been reported, especially from mid-1990s. Though many works have been investigated, the unexpected
scientic growth of CRP contrasts with few commercially available products derived from these
techniques. But, for uoropolymers, the situation appears reversed since iodine transfer polymerization
of uoroalkenes already yielded commercially available thermoplastic elastomers as soon as 1984. These
proceedings display a brief overview or CRP of uorinated monomers (with a real challenge for gaseous
uoroalkenes such as vinylidene uoride, chlorotriuoroethylene, 3,3,3-triuoropropene, hexauoropropylene, peruoromethyl vinyl ether). These monomers can be (co)polymerized via the iodine
transfer polymerization or from techniques that involve either borinates or xanthates (named MADIX).
These technologies enable one to generate copolymers that exhibit well-dened architectures, such as
telechelic, block and graft copolymers and open up High Tech applications such as potentially nonbioaccumulable surfactants, elastomers endowed with low Tgs and that can be crosslinked,
thermoplastic elastomers which can be used in a wide range of temperatures, fuel cell membranes
being processed either by casting or by reactive extrusion.
2014 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Keywords:
Controlled radical (co)polymerization
Fluorinated elastomers
Fluoroalkenes
Fuel cells
Surfactants
Vinylidene uoride

1. Introduction
Fluorinated (co)polymers [15] are remarkable niche specialty
macromolecules because of (i) their unique combination of
exceptional properties (mainly linked to the low polarisability,
the strong electronegativity, and the small Van der Waals radius
(1.32 A) of the uorine atom, and to the strong CF bond (that bond
energy dissociation worths 485 kJ/mol) and (ii) their wide variety
of morphologies that range from plastomeric, elastomeric,
thermoplastic, to thermoplastic elastomeric, so that they can have
a semi crystalline or totally amorphous structure. Hence,
uoropolymers that contain a high uorine contents in the
polymeric backbone display high thermal, chemical, aging and
weather resistances, unique inertness to solvents, hydrocarbons,
acids, and to alkalies, and exhibit low ammability, refractive
index, dielectric constants, and low moisture absorption while
polymers bearing a peruorinated dangling group exhibit surface

* Tel.: +33 467 144 368; fax: +33 467 147 220.
E-mail address: bruno.ameduri@enscm.fr

energy (oil and water repellency). Furthermore, the strong CF


bond provokes a crucial effect on the improvements of resistances
to oxidation and hydrolytic decompositions.
Most uorochemicals arise from calcium uoride (also called
uorspar, uorite, or uor mineralis) [6]. Major ressources are
located in South Africa, China, and Mexico [6]. Addition of sulfuric
acid onto that mineral leads to acid uoride (Scheme 1) that further
enables uorination or various (chlorinated) intermediates to get
uorocompounds.
For all such exceptional properties above, these specialty
macromolecules [15] have found many applications in High
Technologies areas: automotive industries (ca. 300 g of uoropolymers per car) uids for transmission [5] and in components of
fuel cells and lithium ions batteries, aerospace and aeronautics
(use of elastomers as seals, gaskets, O-rings for use in extreme
temperatures for tanks of liquid hydrogen or hydrazine in boosters
of space shuttles [5,6]), petrochemical (pipes and coatings as
liners), microelectronics, chemical engineering (high performance
membranes [7]), textile treatment, building (paints and coatings
resistant to UV and to grafti and stone protection, especially
coatings of old monuments for the Cultural Heritage [8]), and

http://dx.doi.org/10.1016/j.jtice.2014.05.012
1876-1070/ 2014 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Please cite this article in press as: Ameduri B. Recent advances in the controlled radical (co) polymerization of uoroalkenes and
applications therefrom. J Taiwan Inst Chem Eng (2014), http://dx.doi.org/10.1016/j.jtice.2014.05.012

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CaF2 (sol) + H2SO4 (liq)

CaSO4 (sol) + 2HF (gas)

+M

Scheme 1. Preparation of acid uoride from calcium uoride.

P X
optics (core and cladding of optical bers [9]). In spite of their high
price (related to the cost of the small scale of fabrication, the
purication and production of the gaseous monomers, and to
unusual processes of polymerization, such as in suspension or
dispersion with specic surfactants or emulsiers), these polymers
have known major developments in modern high-tech technologies.
As a matter of fact, uorinated homopolymers may display
various limitations: (i) high crystallinity (PTFE is ca. 95%
crystalline) thus induces a poor solubility in common organic
solvents, and (ii) difcult curing or crosslinking. [10] Thus, a
further generation of uorinated macromolecules, copolymers
[4,5,1012], has been extensively developed from the 19501960s
without displaying such homopolymers disadvantages. Actually,
these copolymers are based on a mixture of various comonomers
that insert side chains or bulky groups (which further induce a
certain disorder in the macromolecule) enabling to decrease or
suppress the high crystallinity of the homopolymer. According to
the function brought by the functional comonomer, the resulting
copolymers (Scheme 2) exhibit various challenging properties and
thus can nd valuable applications in specic areas.
Fluoropolymers based on uoroalkenes are synthesized from
conventional radical methods of polymerization [16] and a few
strategies of controlled radical polymerization (CRP) have successfully been applied on uoroalkenes [13]. Actually, CRP has
undergone a growing development [14] as a useful tool to precisely
predict the molar masses and to control polymeric structures, as
well as getting narrow polydispersities. This arises from the nature
of the (macro)radicals (that have very short life times), the fast
equilibrium between living macroradicals and dormant chains
(Scheme 3), and to avoid termination and transfer reactions in
certain conditions. Many books and reviews have reported and
summarized the exceptional and inventive development of
modern techniques of CRP of monomers.
The major benet of such methods is the possibility of tailoring
well-dened polymers (telechelic, block, graft, or star copolymers)
by convenient radical polymerizations.
Though many basic studies have been reported, industrial
realizations have already demonstrated that such a technique is
also revelant for the productions of adhesives, dispersants,
lubricants, high-performance elastomers, etc., and can also nd
much interest in novel electrical [15], optical [16], and biomedical
materials [17]. More than 13,000 papers have been published on
CRP over the last 20 years, and the industrial interest is based on an
anticipated $20 billion/year market for materials achieved by CRP
[18]. Nowadays, uorinated thermoplastic elastomers, based on
Hard-b-Soft-b-Hard triblock copolymers, still involved in electronics, aerospace, automotive industries and medical applications
[19,20], are currently produced at the industrial scale, linked by the

n H2C=CF2
(VDF)

X
Z
p C=C
Spacer
Y

kp

k act

dormant
chains

P
k deact
active chains
(propagating)

Scheme 3. Fast equilibrium between active macroradicals and dormant chains in


the controlled radical (co)polymerization.

fascinating discovery in the late 1970s by Tatemoto working at the


Daikin company [21].
Hence, it was of interest to supply more recent results on those
achieved from controlled radical polymerization and this proceeding article rst briey summarizes the different strategies of CRP,
then a summary of surveys on CRP of uorinated alkenes will be
briey mentioned, taking into account that a more exhaustive
review on CRP of uorinated monomers (including styrenic and
(meth)acrylic ones) was published four years ago [13]. Finally,
applications of such well-designed (co)polymers will be supplied.
2. Strategies of controlled radical (co)polymerization
Since the mid-1990s, the international research activity in the
eld of controlled (or pseudoliving) radical polymerization (LRP)
has considerably grown [14]. The general principle of the methods
reported so far is based on a fast reversible activation-deactivation
equilibrium between dormant chains (or dead chains) and active
chains (or propagating radicals), as in Scheme 3.
Many textbooks and reviews (few of them are supplied below)
have well summarized. One of the oldiest techniques, iodine
transfer (co)polymerization, was pioneered by Tatemoto [21], and
was rst applied on uoroalkenes. It was followed by the iniferter
method [22] (where iniferter means INItiation-transFER-TERmination) introduced by Otsu in 1982. Then, more recent ones have
been reported and reviewed such as nitroxide-mediated radical
polymerization (NMP) [23], atom transfer radical polymerization
(ATRP) [24], reversed iodine transfer polymerization [25], reversible addition-fragmentation chain transfer (RAFT) [26] including
macromolecular design via interchange of xanthates (MADIX) [27],
organoheteroatom mediated radical polymerization [28,29] involving Tellurium (TERP), Bismuth, Antimony derivatives developed by Yamago [28] (Scheme 4), or Cobalt mediated radical
polymerization (CRMP) in the presence of bis(acetylacetonato)cobalt(II) (Co(acac)2) [29]. In addition, CRP controlled by borinate
derivatives under a recombination process from Chung [30], and
more recent methods developed by Goto et al. [31] have already
shown a great interest, briey summarized in Scheme 5.
Though uorinated alkenes have been involved in radical
polymerization controlled by boron derivatives, [30] to the best of
our knowledge, no study on TERP or CRMP have been attempted on
uoromonomers.
As known, CRP tends to avoid any termination reactions,
though, as expected classical recombination/disproportionation

X Z

rad.
conv. or controlled

X,Y,Z : H,F,CF3
G : Functional Group

(VDF)x C C
Y Spacer
G

Scheme 2. Radical copolymerization of vinylidene uoride (VDF) with


uorofunctional comonomers (where G stands for SO3H, P(O)(OEt)2, Br, CO2H,
oligo(ethylene oxide), Si(OEt)3, NR3+) [12].

Scheme 4. Radical polymerizations mediated by tellurium, antimoiny and bismuth


derivatives [28].

Please cite this article in press as: Ameduri B. Recent advances in the controlled radical (co) polymerization of uoroalkenes and
applications therefrom. J Taiwan Inst Chem Eng (2014), http://dx.doi.org/10.1016/j.jtice.2014.05.012

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Scheme 5. Radical chain transfer catalyzed polymerization [31].

rates are noted for uorinated monomers (styrenic and (meth)acrylates). Nevertheless, for uoroalkenes, recombination is exclusively observed [32].
Actually, various uorinated organic compounds (such as
initiators, monomers, chain transfer agents, or solvents) have
been reported in living radical polymerization [33] considering the
advantages of steric and electronic effects, to serve as labeling
agents, or to induce specic properties. A previous review [13]
browses that state of the art of the CRP of uorinated monomers
and these present proceedings update recent results on CRP of
uoroalkenes only.
3. Controlled radical polymerization of uoroalkenes
3.1. Iodine transfer polymerization of uoroalkenes
3.1.1. History and production of copolymers produced by ITP
Iodine transfer polymerization (ITP) is an extension of the
telomerization [34] and a quasi exhaustive update review on the
radical telomerization of uoroalkenes is included in a chapter of a
book [4]. Indeed, in the late 1970s, Tatemoto pionneered the smart
concept of the controlled radical copolymerization and presented
for the rst time the iodine transfer (co)polymerization of
uoroalkenes, especially on vinylidene uoride, during a SovietJapanese Conference [21a] after two patents were deposited by
Daikin in 1978 [19].
Various uorinated monomers (such as vinylidene uoride,
VDF, tetrauoroethylene, TFE, and hexauoropropylene, HFP) have
been successfully used in ITP. The active pseudoliving center,
generally located in the end groups of the growing polymer, has the
same reactivity at any time during polymerization even when the
reaction is stopped [13,35]. In the case of ITP of uoroalkenes, the
terminal active bond is always the CI bond that originates from
the initial iodine-containing chain transfer agent and monomer, as
displayed in Scheme 6.
The control of that reaction was evidenced from the high
transfer rate (ctr = 7 at 74 8C [36]) which is faster than the
termination rate since, as mentioned above, it is known that latter
step of most uoroalkenes proceeds exclusively through recombination [32].
Tatemoto et al. [21] used peroxides as initiators of polymerization in solution involving usually peruorinated or chlorouorinated solvents. Improvement was also possible by using diiodo[21,37] and polyiodo-compounds [21]. In addition, basic approach

CnF2n+1 I

(p + 1) H2C=CF2

R or

CnF2n+1 (C2H2F2)p CH2CF2 I

Scheme 6. Iodine transfer polymerization of vinylidene uoride in the presence of


1-iodoperuoroalkanes as the chain transfer agents.
Reproduced with permission from Amer. Chem. Soc. [13].

of that thechnique was studied either by Apostolos group [35] on


the kinetics of radical copolymerization of VDF and HFP or by our
team on ITP of VDF in the presence of various 1-iodouoroalkyl
chain transfer agents (CTA). Their structures induced a drastic
effect onto the controlled behavior of the reaction since C6F13I or
C6F13CH2CF2I enabled a pseudoliving tendancy [36] (thanks to the
lability of CF2-I bond and the fast decomposition of the
peruorohexyl iodide) while HCF2CF2CH2I did not favor any
control of ITP [36]. However, CRP of unsymmetrical uoroolen
(such as VDF) highlighted that defects of VDF chaining occured as
soon as 1215 VDF units were incorporated in resulting PVDF thus
limiting the reactivation of -CF2CH2-I in these conditions, making
broader the polydispersity indices.
Though it is scaled up with difculties, a similar ITP was
achieved by Beuermanns group [38] in a different medium
(supercritical CO2 that was reported to solubilize uoropolymers
[39]) at 120 8C and 1500 bar, in homogeneous phase and in the
presence of C6F13I [38a] or IC6F12I [38b] with narrow polydispersity indices (1.21.5).
More recently, Asandei et al. [40] used a photocatalyzed process
of the controlled radical polymerization of VDF initiated in the
presence of Mn2(CO)10 and a wide range of solvents, dimethyl
carbonate (DMC) was regarded as the most suitable one. Although
this procedure is limited to academic Lab, these interesting results
opened up to the preparation of a wide range of PVDF-b-poly(M)
block copolymers (where M0 stands for vinyl acetate, vinyl
chloride, acrylonitrile, methyl acrylate, and butadiene).
In addition, the same team used (CX3CO2)2IIIIPh as efcient
photoinitiators for the CRP of VDF with external [I(CF2)6I] and in
situ generated (CF3I) iodinated chain transfer agents that also
produce PVDF-b-poly(M0 ) block copolymers (where M0 stands for
styrene, butadiene, 2,2,2-triuoroethyl methacrylate, and methylacrylate [41].
Actually, block copolymers achieved from ITP, also pioneered
by Tatemoto et al. [19] in the early 1980s and these Japanese
researchers synthesized PVDF-b-poly(VDF-co-HFP)-b-PVDF block
copolymers by iodine transfer copolymerization of VDF and HFP in
the presence of an a,v-diiodoperuoroalkane (IC4F8I or IC6F12I)
which generated a rst elastomeric soft block. This resulting soft
macromolecular diiodides further initiate the ITP of VDF (or
ethylene and TFE) to yield such Hard-b-Soft-b-Hard triblock
copolymers. The applications of these thermoplastic elastomers
(TPEs), can be processed as O-rings, hot melts, pressure-sensitive
adhesives, tough transparent lms, sealants that exhibit good
chemical and aging resistances for aerospace, aeronautics,
engineering and automotive industries, as well as protective
coatings of metals, or in specic applications such as dental plates
or in optics. These TPEs marketed by the Daikin Company as soon
as 1984, under the Daiel1 trademark, are composed of soft
segments (low Tg blocks containing the poly(VDF-co-HFP) as above
or poly(VDF-co-CTFE), poly(VDF-ter-HFP-ter-TFE), poly(E-terPMVE-ter-TFE) elastomeric blocks, where E and PMVE stand for
ethylene and peuoromethyl vinyl ether, respectively) and hard
blocks composed of various crystalline sequences (PVDF) to get
Dai-el1 T-630) [19,42], PTFE, or poly(ethylene-alt-tetrauoroethylene) or poly(E-ter-TFE-ter-HFP) hard block (Dai-el1 T530)
thermoplastics) [42]. Several years later, these TPEs were also
produced by Ausimont (now Solvay Specialty Polymers, from the
Pseudo Branching and Living Technology) and DuPont, under the
Tecnoon1 and Viton1 tradenames, respectively.
3.1.2. Copolymers based on VDF and peruoroalkyl vinyl ethers
Though peruoroalkyl vinyl ethers (PAVEs) do not homopolymerize (rPAVE = 0), they can easily copolymerize with either TFE or
VDF to yield random copolymers endowed with a crystallinity rate
lower than those of PTFE and PVDF [43]. From ca. 20% PAVE the

Please cite this article in press as: Ameduri B. Recent advances in the controlled radical (co) polymerization of uoroalkenes and
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C 4F8

a CH2

CF2

b CF2

copolymerization of VDF and PMVE was evidenced by the linear


molar masses-monomer conversion relationship [45]. In addition,
from the signals assigned to central C4F8 group arising from the CTA,
19
F NMR spectroscopy allowed us to determine the molecular
weights and to well identify the end groups (exclusively composed
of VDF-I) [45].
The resulting poly(VDF-co-PMVE) copolymers were endowed
with low Tg values (ca. 60 8C) and satisfactory thermal stability
when they could be crosslinked. That crosslinking was achieved
from rst the chemical modication of these diiodides into original
telechelic bis(hydroxyl) [46], diazido [47], diacrylates [46],
bis(triethoxysilanes) [48], bis(methyldiethoxysilanes) [48]
poly(VDF-co-PMVE) copolymers,

CF
OCF3

CF2]z I

I [(CF2CH2)x CF2 CF]y C4F8 [(CF-CF2)w CH2


OCF3

OCF3

Scheme 7. Iodine transfer copolymerization of vinylidene uoride (VDF) with


peruoromethyl vinyl ether (PMVE) in the presence of 1,4-diiodoperuorobutane
chain transfer agent.
Reproduced with permission from Amer. Chem. Soc. [45].

3.1.2.1. Telechelic di(meth)acrylates based on poly(VDF-co-PMVE)


copolymers. Scheme 8 illustrates the straightforward strategy to
obtain telechelic photocrosslinkable diacrylates [46]. Crosslinked
lms were obtained from Darocur1 1173 photoinitiator (PI,
Scheme 9) that showed a good efciency while Irgacure1 879 PI
was suitable for monolithic networks (23 mm depth). After
photocrosslinking, the resulting materials possessed Tg that
reached 48 to 42 8C and could swell up to 35% only, after
immersion in boiling octane for 48 h.

resulting copolymers exhibit elastomeric properties. Indeed, the


innovation lies on synthesizing materials endowed with Tgs lower
that 40 8C for low temperature resistance (or resilience)applications [44] and with good thermal stability, as valuable
candidates involved in aeronautic and automotive industries.
In contrast to numerous publications and patents [43] that
disclose successful conventional radical copolymerizations of VDF
(or TFE) and PAVEs, only one patent and publication mention the CR
copolymerization of VDF with peruoromethyl vinyl ether (PMVE)
via the ITP process in the presence of C6F13I or a,v-diiodoperuoroalkanes as the chain transfer agents [45] (Scheme 7) in water,
without any surfactant. This controlled (or pseudoliving) radical

ICH2 CH2

CF2

C
H2

y CF

CF2

3.1.2.2. Synthesis of organic/inorganic hybrid materials. These


poly(VDF-co-PMVE) cooligomers wre also involved in the formation of hybrid organic/inorganic (O/I) networks achieved from the

(CF2 )4 CF2

CF

OCF3

C
H2

CF2 y
x

CH2 CH2I

OCF3

DMF/H20
120C

HOCH2 CH2

CF2

C
H2

y CF

CF2

(CF2 )4 CF2

OCF3

CF

C
H2

CH2 CH2OH

CF2 y
x

OCF3

O
OCH2CH2

CF2

C
H2

y CF

CF2

(CF2) 4 CF2

CF

OCF3

C
H2

CF2 y
CH2CH 2O
x

OCF3
H2SO4 /MeOH
25C

HOCH2CH 2

CF2

C
H2

y CF

CF2

(CF2)4 CF2

OCF3

C
H2

CF2 y
CH 2CH2 OH
x

OCF3

Cl

CF

RT/Ionol
CH3CN

O
C2H4

VDF-co-PMVE

C2H4
O

Scheme 8. Synthetic pathway for the conversion of telechelic diiodo poly(VDF-co-PMVE) copolymer to telechelic diols and to diacrylates [46].

Please cite this article in press as: Ameduri B. Recent advances in the controlled radical (co) polymerization of uoroalkenes and
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Scheme 9. Conversion of diacrylates to crosslinked networks via UV sensitive radical initiator reproduced with permission from Amer. Chem. Soc. [46].

diazido poly(VDF-co-PMVE) copolymer was catalyzed by CuBr


complexed by bipyridine [47], as shown in Scheme 11.

hydrolysis and subsequent polycondensation of terminal siloxane


functional groups. First, the successful functionalization of the
telechelic diiodopoly(VDF-co-PMVE) copolymer by its radical
addition onto vinyl poly(ethoxy)silane (Scheme 10) allowed the
formation of hybrid O/I networks via hydrolysis and polycondensation (solgel). Each experiment for network formation required a
specic catalyst and solvent [48].
Information concerning the physical requirements needed for
desirable solgel network can be gained from the issue of phase
separation raised as being undesirable and the concept of using an
alternative to siloxane was disclosed (use of Ti, Zr, Al complexes as
opposed to Si for the exible yet strong inorganic cross-link
Fig. 1). Solgel either copolycondensed or via Huisgen reaction (or
click chemistry, Scheme 11), led to various materials (Fig. 2), the
thermal, swelling and mechanical properties of which were
assessed.

3.1.3. Iodine transfer copolymerization of alkyl 2triuoromethacrylates and uoroalkene(s)


2-Triuoromethacrylates can be homopolymerized under
anioninc initation [49], in contrast to unefcient radical homopolymerization [50], unless under specic conditions [51]. The
controlled radical copolymerization of uoroalkenes with Facrylates is scarce since uoroalkenes are less reactive than
acrylates or methacrylates, because of their too low Q value with
respect to that of (meth)acrylates. However, the iodine transfer
copolymerization of VDF with either 2-triuoromethacrylic acid
(MAF) [52] or 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecauorooctyl 2-(triuoromethyl methacrylate [52c] in the presence of C6F13I or
CF3I, respectively, and the terpolymerization of VDF with HFP and
MAF [53] achieved in emulsion, initiated by a persulfate, in the
presence of IC6F12I as the chain transfer agents but without any
surfactant (Scheme 12) were successful. Subsequently, the
poly(VDF-ter-HFP-ter-MAF) terpolymers were involved with

3.1.2.3. Step growth polymerization and click chemistry. The


Huisgens 1,3-dipolar cycloaddition in the polymerization of
a,v-dipropargyl ether hexauorobisphenol AF with telechelic

R'''
I

CF2

C
H2

y CF

CF 2

(CF2)4 CF2

CF

C
H2

CF2 y
I
x

H 2C

C
H

Si

R''

R'
OCF3

OCF3
O
O
O

H 3C

R'''

R'''
R''

Si
R'

CHI

C
H2

CF2

C
H2

y CF

CF2

(CF 2)4 CF 2

CF

C
H2

CF2 y
C CHI
x H
2

Si

R''

R'
OCF3

OCF3

Scheme 10. Reaction scheme for the functionalization of telechelic diiodo poly(VDF-co-PMVE) copolymer with poly(alkoxy)silanes; R0 = OEt, R00 = Me or OEt and R000 = Me [48].

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B. Ameduri / Journal of the Taiwan Institute of Chemical Engineers xxx (2014) xxxxxx

Fig. 2. Crosslinked samples based on poly(VDF-co-PMVE) copolymer (Tg = 38 8C


and T10 = 350 8C [48].

the selective reduction of chlorine atoms in chlorotriuoroethylene (CTFE) units in poly(VDF-co-CTFE) copolymers to yield
poly(VDF-ter-CTFE-ter-TrFE) terpolymers (where TrFE stands for
triuoroethylene).
3.3. Macromolecular design through interchange of xanthate
(MADIX) or radical (co)polymerization controlled by xanthates
Fig. 1. Schematic representation of a typical hybrid organicinorganic network,
where X represents the inorganic phase (in this instance it could be silicate or
titanate) and the organic phase is represented by poly(VDF-co-PMVE) copolymer.
The distance between inorganic phases is provided as 1/s.

nanosilica to lead to original uoropolymer/nanosilica nanocomposites [53] endowed with very high thermal properties.
Furthermore, these terpolymers were mixed with a poly(styrene)-b-poly(2-vinylpyridine)-b-poly(ethylene oxide) triblock terpolymer (PS-b-P2VP-b-PEO) to lead to interesting micellar
structures as coreshells [54]. They were made of a core formed
of poly(VDF-co-HFP) sequences and MAF/P2VP hydrogen-bonded
complexes and a corona of PS and PEO chains. The micelles
average radii based on PS-POE/poly(VDF-ter-HFP-ter-MAF) terpolymers were ranging between 13 and 31 nm [54].
3.2. Radical polymerization of uoroalkenes controlled by alkylboron
compounds
Chungs team [30,55] used his expertise on boron chemistry to
report another method allowing the radical (co)polymerization of
VDF that requires alkylboron compounds activated by oxygen. BR3
borane reacts with oxygen to produce RO-OBR2 that spontaneously
yields RO radicals (as an oxygen centered radical that can initiate
the (co)polymerization of VDF and CTFE) and OBR2 borinate (too
stabilized and, consequently, acts as an efcient counter radical
which traps any macroradical by recombination). That strategy
was smartly applied to design piezoelectrical polymers [56] after

Besides ITP and process involving borinates, another strategy


close to RAFT polymerization involves a xanthate as a controlling
agent (pioneered by the Rhodia Company [20,27] as the most
suitable process to control the radical polymerization of vinyl
acetate, VAc) that has been successfully applied for the (co)polymerizations of uoroalkenes, such as (i) VDF with three different
comonomers: 3,3,3-triuoropropene (TFP), PMVE, and more
recently, tert-butyl 2-triuoromethyl acrylate (MAF-TBE) and (ii)
chlorotriuoroethylene (CTFE) with vinyl ethers.
3.3.1. MADIX (co)polymerizations of VDF
A uorinated xanthate, C6F13C2H4OCOCH(CH3)SC(S)OEt, was
rst synthesized and then successful tested in the MADIX
polymerization of VAc [57]. Then, this halogenated xanthate
was also efcient to control the radical copolymerization of VDF
and TFP [57] (Scheme 13). These resulting uorinated poly(VDFco-TFP) copolymers that bear a xanthate end-group, regarded as
macroxanthates, were able to further allow a chain extension by a
MADIX polymerization of VAc to yield original poly(VDF-co-TFP)b-oligo(VAc) block copolymers (Scheme 13).
The oligo(VAc) blocks were hydrolyzed under acidic conditions
to yield hydrophilic sequences thus turning the resulting
poly(VDF-co-TFP)-b-oligo(vinyl alcohol) diblock copolymers
amphiphilic, that hence acted as novel surfactants [57] endowed
with low critical micellar concentrations and surface tensions
(17 mN/m for 0.5% of copolymer) (Fig. 3) almost as low as those of
commercially available PFOA. Actually, uorosurfactants are much
more efcient than their hydrogenated homologues [58] by their
lower surface tensions. They can be found in more than 200
applications in re ghting foams, paints, cosmetics, detergents,
etc. But, commercially available peruorooctanoic acid (PFOA) and

C6F12

H2C

CF2

F2C

CF
CF3

Scheme 11. Condensation of telechelic uorinated diazido compound with


aromatic a,v-diyne (RF,H = C6F12 or C2F4CH2CF2CF2CF(CF3)).
Reproduced with permission from Amer. Chem. Soc. [47].

(CF2CH2)

CF3
x

CFCF2
CF3

H2C

CF3
COOH

CF3
C6F12

CH2
COOH
n

H2C

CF2CF
COOH CF
3

(CH2CF2)

I
m

Scheme 12. Iodine transfer terpolymerization of vinylidene uoride with atriuoromethacrylic acid and hexauoropropylene in the presence of 1,6diiodoperuorohexane [53].

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Scheme 13. Sequenced MADIX terpolymerization of vinylidene uorine (VDF), 3,3,3-triuoropropene (TFP), and vinyl acetate (VAc) controlled by a uorinated xanthate for
the synthesis of poly(VDF-co-TFP)-b-oligo(VAc) block copolymers further hydrolized into original surfactants [57].

Fig. 3. Surface tension and conductimetry curves of poly(VDF-co-TFP)-b-oligo(VA) block cooligomers (diamonds) compared to those of ammonium peruorooctanoate
(triangles); VDF, TFP, and VA stand for vinylidene uoride, 3,3,3-triuoropropene, and vinyl alcohol, respectively [57].

peruorooctane sulfonic acid (PFOS) are toxic, persistent and


bioaccumlulable (and even suspect to be mutagenic) because of
their small size and the high stability of the peruorinated groups.
Their half lives in the human serum are estimated to ca. 3.8 and 5.4
years, respectiviely [59], and these surfactants are spread all over
the Earth and oceans, rivers, and wild life (including sh, birds and
mammals) [60,61]. Hence, the challenge lies in nding alternatives
that can be enzymatically or metabotically degradable and thus
inserting weak points such as ether linkages [62] or methylene
groups has been possible.
In addition the xanthate was also successfully used to prepare
surfactants for supercritical CO2 media, in which uorinated
elastomeric sequence showed an interesting CO2-philicity behavior. NMR spectroscopy and SEC characterization (Fig. 4) got good
evidence of the obtaining of block copolymers [63] (Scheme 14).
SEC chromatograms of the rst PDMA block and the PDMA-bpoly(VDF-co-PMVE) diblock (Fig. 4) clearly evidenced the chain
extension by the increase of molar masses and the presence of a
negative signal assigned to low refractive index of uorinated
copolymers.
A similar strategy was successfully applied to the radical
copolymerization of tert-butyl 2-triuoromethacrylate (MAF-TBE)
with vinylidene uoride (VDF), initiated by bis (4-tert-butyl
cyclohexyl) peroxydicarbonate and controlled by O-ethyl-S-(1methyloxycarbonyl) ethyl xanthate as a chain transfer agent (CTA)
(Scheme 15). Molar masses ranged between 1500 and 40,000 g/
mol while polydispersity indices (PDIs) were lower than 1.8 (Fig. 5)
from optimized conditions taking into account use of various
radical initiators, solvents, initial reactant molar ratios [64]. These

poly(VDF-co-MAF-TBE) copolymers bearing a xanthate end-group


were further chain extended by either an oligo(VAc) or a PVDF
second blocks leading to poly(VDF-co-MAF-TBE)-b-poly(VAc) and
poly(VDF-co-MAF-TBE)-b-PVDF block copolymers, respectively.

Fig. 4. Overlays of SEC chromatograms for the RAFT/MADIX polymerization of VDF


and PMVE from an oligo(dimethyl acrylamide) PDMA macromolecular agent
(400 g/mol) in DMF (refractive index detector) reproduced with permission from
Amer. Chem. Soc. [63].

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B. Ameduri / Journal of the Taiwan Institute of Chemical Engineers xxx (2014) xxxxxx

O
S

O
S

tBP P i, 74 C, 4 h

F F

1,1,1,3,3-pentafluorobutane

n = 0 , 4, 8.

n
N

F
O

F O
F 3C

O
S

n = 0, 4, 8.

Scheme 14. RAFT/MADIX copolymerization of vinylidene uorine (VDF) and peruoromethyl vinyl ether (PMVE) from a macroxanthate based on oligo(N,N-dimethyl
acrylamide) for the synthesis of block copolymers reproduced with permission from Amer. Chem. Soc. [63].

Scheme 15. Radical copolymerization of vinylidene uoride (VDF) with t-butyl 2-triuoromethacrylate (MAF-TBE) controlled by O-ethyl-S-(1-methyloxycarbonyl) ethyl
xanthate.
Reproduced with permission from Royal Soc Chem. [64].

Interestingly, these copolymers have been successfully used as


original compatibilizers for achieving new poly(VDF-co-HFP)
copolymer/functional silica nanocomposites as novel PEMFC
[65]. These composites were synthesized through in situ generation of the inorganic phase (via solgel chemistry from mercaptopropylethoxysilane) by reactive extrusion. The optimization of this
proton conductivity being deeply linked to the materials morphology (diameter of the inorganic domains below 1 mm), it was
crucial to synthesize and to incorporate such compatibilizer
copolymers between both organic and inorganic phases. The
resulting composites bearing mercaptan functions had to be
oxidized into SO3H groups. Thanks to a control of the processing
and to the synthesis parameters, original nanocomposites as fuel
cell membranes have been prepared from uorinated polymers
and silica-SH (15 wt%). These membranes displayed theoretical IEC
of 2 mequiv./g. (Experimental IEC ranged between 1.0 and
1.3 mequiv./g). Their proton conductivities reached 3040 mS/
cm at room temperature and 100% RH, while their water swelling
rates were lower than that of Naon1 212 [65].

rst started from the conventional radical copolymerization of VDF


and HFP initiated by a functional telechelic initiator to lead to a
telechelic poly(VDF-co-HFP) copolymer. The resulting copolymer
was functionalized into a macro-CTA for a subsequent RAFT
polymerization of the methacrylate imidazolium. The authors
observed that the compatibility of the IL and uoropolymer matrix
likely prevents discrete microphase separation in the triblock
copolymers. The polymers with triuorosulfonate counterions
displayed higher ionic conductivities than their BF4 homologues
due to the enhanced polymer segmental mobility. The temperature
dependence of the ion mobilities of the triblock copolymers
was well described using a VogelTammanFulcher equation,

3.3.2. MADIX the copolymerizations of chlorotriuoroethylene


The same strategy was also used by Liu et al. [66] who
synthesized poly(CTFE-alt-vinyl ethers)-b-oligo(VAc) block copolymers in a two-step procedure (a controlled radical alternated
copolymerization of CTFE with a vinyl ether followed by a chain
extension with a poly(VAc) second block) controlled by O-ethyl-S(1-methyloxycarbonyl) ethyl xanthate. However, neither properties nor applications were supplied.
3.4. RAFT (co)polymerization controlled by trithiocarbonates
Wangs team [67] reported the synthesis of a series of
uoropolymer based triblock copolymers with pendant imidazolium cations as ionic liquid (IL)-containing polymers. That strategy

Fig. 5. Number-average molar mass, Mn (black diamonds), polydispersity index,


Mw/Mn (cross) versus conversion of the sum of monomers (the straight line
represents the evolution of the theoretical number-average Mn).
Reproduced with permission from Royal Soc Chem. [64].

Please cite this article in press as: Ameduri B. Recent advances in the controlled radical (co) polymerization of uoroalkenes and
applications therefrom. J Taiwan Inst Chem Eng (2014), http://dx.doi.org/10.1016/j.jtice.2014.05.012

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B. Ameduri / Journal of the Taiwan Institute of Chemical Engineers xxx (2014) xxxxxx

indicating a strong correlation between ion conduction and


polymer segmental dynamics [67].
4. Conclusions
Thanks to their exceptional properties, uoropolymers have
been used in many High Tech applications. Most uorinated
alkenes are gas and can be (co)polymerized under conventional
radical conditions according to classical processes (emulsion,
dispersion, suspension, and solvent). Though CRP of uoroalkenes
is even trickier, this technique has been investigated by both
industries and academia, and, so far, only three successful attempts
are iodine transfer polymerization (ITP), macromolecular design
through interchange of xanthate (MADIX) and in certain conditions
by boron species. Moreover, various original well-designed
architectures of these uoropolymers have been produced:
telechelics especially from ITP in the presence of a,v-diiodoperuoroalkane chain transfer agents, alternating copolymers, as
evidenced in the poly(VDF-alt-MAF or MAF-TBE) copolymers, graft
copolymers from ATRP of poly(VDF-co-CTFE) copolymers [68], and
block copolymers [13]. These latters led to new electrolytes with
high conductivities [67] or thermoplastic elastomers (TPEs) that
have aready reached an industrial scale-production; (Daiel1,
Tecnoon1, and Viton1 marketed by Daikin, Solvay Specialty
Polymers, and DuPont Performance Elastomers, respectively [19]).
The produced uorocopolymers have found many applications:
thermoplastics, elastomers, or TPEs for automotive, aerospace,
aeronautics industries (e.g., elastomeric sealants, O-rings, gaskets
which are resistant to low and high temperature, in aggressive
media), energy (fuel cell membranes, lithium ion batteries,
actuators, and piezoelectrical devices), microltration and ultraltration membranes, blends, nanocomposites, and as surfactants
that should meet the requirement of non-toxicity, non-persistency
and non-bioaccumulation. It is expected that new uoropolymeric
materials and new curing chemistry [5,10,69] will be developed in
the future, due to severe service conditions undergone by the
resulting materials, low temperature resilience, and resistance to a
broad range of temperatures. Hence, CRP can be regarded as a
relevant method to produce future well designed specialty
uorinated (co)polymers.

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Acknowledgements
The author thanks Professor B. Boutevin for stimulating inputs,
Professor G. Kostov and M. Destarac, as well as post-doc
researchers and PhD students (mentioned as co-authors in the
list of references). Industrial companies and colleagues are also
granted for fruitful discussions and for building valuable collaborations and/or for sponsoring various studies and/or supplying
free samples, the French National Agency (ANR, PREMHYS
project)), GDR Pile a` Combustible & Systemes, and several
Industries (especially Dr M.H. Hung from DuPont Performance
Elastomers, Dr Kawada from Tosoh F-Tech company and Great
Lakes/Chemtura).
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Please cite this article in press as: Ameduri B. Recent advances in the controlled radical (co) polymerization of uoroalkenes and
applications therefrom. J Taiwan Inst Chem Eng (2014), http://dx.doi.org/10.1016/j.jtice.2014.05.012