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Journal of The Taiwan Institute of Chemical Engineers Volume 45 Issue 6 2014 (Doi 10.1016/j.jtice.2014.05.012) Ameduri, Bruno - Recent Advances in The Controlled Radical (Co) Polymerization of Fluo
Journal of The Taiwan Institute of Chemical Engineers Volume 45 Issue 6 2014 (Doi 10.1016/j.jtice.2014.05.012) Ameduri, Bruno - Recent Advances in The Controlled Radical (Co) Polymerization of Fluo
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
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
G Model
+M
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)
X Z
rad.
conv. or controlled
X,Y,Z : H,F,CF3
G : Functional Group
(VDF)x C C
Y Spacer
G
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
G Model
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
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
G Model
C 4F8
a CH2
CF2
b CF2
CF
OCF3
CF2]z I
OCF3
ICH2 CH2
CF2
C
H2
y CF
CF2
(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
applications therefrom. J Taiwan Inst Chem Eng (2014), http://dx.doi.org/10.1016/j.jtice.2014.05.012
G Model
Scheme 9. Conversion of diacrylates to crosslinked networks via UV sensitive radical initiator reproduced with permission from Amer. Chem. Soc. [46].
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].
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
G Model
B. Ameduri / Journal of the Taiwan Institute of Chemical Engineers xxx (2014) xxxxxx
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
C6F12
H2C
CF2
F2C
CF
CF3
(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].
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
G Model
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].
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
G Model
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].
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
G Model
[18]
[19]
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