Fluoroelastomers - Synthesis, Properties and Applications

Prog. Polym. Sci.
26 (2001) 105±187
www.elsevier.nl/locate/ppolysci
Fluoroelastomers: synthesis, properties and applications

B. AmeÂduri a,*, B. Boutevin a, G. Kostov b
a
Laboratory of Macromolecular Chemistry, Ecole Nationale SupeÂrieure de Chimie de Montpellier,
UMR Ð CNRS 5076, 8, Rue Ecole Normale, 34296 Montpellier Cedex 5, France
b
University of Bourgas, Center for Electron Beam Technology and Polymers, 8010 Bourgas, Bulgaria
Received 1 June 2000; revised 10 November 2000; accepted 27 November 2000
Abstract
The review seeks to cover recent developments in the area of ¯uorinated elastomers. It reports that, except for
isolated cases, most ¯uoroelastomers are synthesized by radical co-, ternary or tetrapolymerizations. Hence, after
reminding the most known syntheses of ¯uoroalkenes involved in the preparation of these ¯uoropolymers and
recent achievements of block, graft and alternating copolymers, several academic laws and concepts (e.g. kinetics)
of the copolymerization are presented. The section dealing with the synthesis of ¯uoroelastomers is divided into
two parts: the ®rst one covers the preparation of ¯uorinated copolymers containing tetra¯uoroethylene, while the
second one extensively describes the preparation of ¯uoroelastomers based on vinylidene ¯uoride. This section
also points out recent syntheses on novel reactive functional tri¯uorovinyl or vinyl ether monomers for easy curing
of original ¯uoropolymers. Then, heteroatom-containing ¯uoroelastomers are brie¯y summarized. Various meth-
ods of curing are reported in the following section while the next one describes ingredients used in formulations of
¯uoroelastomeric systems. This review also covers compounding and processing of this class of ¯uoropolymers.
Finally, a summary of various properties and applications of ¯uoroelastomers is presented showing how such
products resistant to severe conditions are useful in modern industries. q 2001 Elsevier Science Ltd. All rights
reserved.
Keywords: Fluoroelastomers; Fluoroalkenes; Copolymers; Cure site monomers; Kinetics of copolymerization; Crosslinking;
Processing; Synthesis±properties relationship; Applications
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
2. Fluoroelastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
2.1. Combination of ¯uoroalkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
2.2. Synthesis of ¯uoroalkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
2.2.1. Vinyl ¯uoride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
* Corresponding author. Tel.: 133-4-67-14-4368; fax: 133-4-67-14-7220.

E-mail address: [email protected] (B. AmeÂduri).
0079-6700/01/$ - see front matter q 2001 Elsevier Science Ltd. All rights reserved.
PII: S0 0 7 9 - 6 7 0 0 ( 0 0 ) 0 0 04 4 - 7
106 B. AmeÂduri et al. / Prog. Polym. Sci. 26 (2001) 105±187
2.2.2. Vinylidene ¯uoride (VDF orVF2) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112

2.2.3. Chlorotri¯uoroethylene (CTFE) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
2.2.4. Tetra¯uoroethylene (TFE) and hexa¯uoropropylene (HFP) . . . . . . . . . . . . . . . . . . . . . . 112
2.2.5. 3,3,3-Tri¯uoropropene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
2.2.6. Fluorinated styrenic monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
2.3. Polymerization of ¯uoroalkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
3. Copolymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
3.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
3.2. Various kinds of ¯uorinated copolymer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
3.2.1. Fluorinated block copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
3.2.2. Fluorinated graft copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
3.2.3. Fluorinated alternating copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
3.3. Kinetics of copolymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
3.3.1. Terminal model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
3.3.2. Penultimate model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
3.3.3. Complex participation model in the acceptor donor copolymerization . . . . . . . . . . . . . . 122
3.3.4. Other copolymerization models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
3.3.5. Q and e parameters and other concepts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
4. Fluoroelastomers from TFE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
4.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
4.2. Fluoroelastomers from TFE and propylene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
4.3. TFE-based ¯uoroelastomers containing ethylene (E) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
4.4. Thermoplastic ¯uoroelastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
4.5. Per¯uoroelastomers from TFE and PAVE monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
4.5.1. Synthesis of comonomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
4.5.2. Copolymerization of TFE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
5. Fluoroelastomers from VDF (or VF2) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
5.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
5.2. VDF/CTFE copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
5.3. VDF/HFP copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
5.4. VDF/penta¯uoropropene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
5.5. VDF/TFE/propylene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
5.6. VDF/tri¯uoroethylene and VDF/hexa¯uoroacetone copolymers . . . . . . . . . . . . . . . . . . . . . . . . . 141
5.7. VDF/PAVE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
5.7.1. Copolymerization of VDF with non-functional PAVE . . . . . . . . . . . . . . . . . . . . . . . . . . 141
5.7.2. Copolymerization of VDF with functional PAVE or PAAVE . . . . . . . . . . . . . . . . . . . . 143
5.8. VDF/functional per¯uorovinyl monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
6. Fluoroelastomers containing heteroatoms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
6.1. Poly(thiocarbonyle ¯uoride)s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
6.2. Fluorinated polyethers and per¯uoropolyethers (PFPEs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
6.3. Fluoro nitroso elastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
6.4. Poly¯uoroalkoxyphosphazene polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
6.5. Fluorosilicones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
7. Crosslinking of ¯uoroelastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
7.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
7.2. Ionic curing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
7.2.1. From amino systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
7.2.2. From bisphenol system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
7.3. Radical curing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
7.3.1. Peroxide curing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
7.3.2. Other system of radical curing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
7.4. Radiation crosslinking of ¯uoroelastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
B. AmeÂduri et al. / Prog. Polym. Sci. 26 (2001) 105±187 107
7.5. Post-curing of ¯uoroelastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156

7.6. Curing chemistry of TFE-based per¯uoroelastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
8. Formulations and ingredients of ¯uoroelastomer compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
8.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
8.2. Vulcanization systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158
8.2.1. Block polyfunctional amines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158
8.2.2. Bisphenolic systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158
8.2.3. Peroxide vulcanization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
8.3. Metal oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
8.4. Fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160
8.5. Processing aids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160
9. Processing of ¯uoroelastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
9.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
9.2. Mixing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
9.2.1. Open mills . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
9.2.2. Internal mixers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
9.3. Molding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
9.3.1. Compression molding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
9.3.2. Injection molding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
9.4. Calendering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
9.5. Extrusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
9.6. Vulcanization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
9.7. Safety and environmental considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
10. Properties of ¯uoroelastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
10.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
10.2. Fluid and chemical resistance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
10.3. Thermal resistance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
10.4. Mechanical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
11. Applications of ¯uoroelastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
12. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
1. Introduction
In contrast to the organic or inorganic ¯uorine chemistries (dating from 1670), that of ¯uorinated
polymers is rather recent: the ®rst discoveries were achieved in the late 1930s with the synthesis of low-
molecular weight polychlorotri¯uoroethylene (PCTFE) [1] followed by that of high-molecular weight
polytetra¯uoroethylene (PTFE) by Plunkett [2] in 1938. Then, several homopolymers were obtained and
further generations of (co)polymers made of various (per)¯uorinated base units were prepared. Nowa-
days, functional polymers bringing new properties have found novel applications and are expanding. A
brief history of the evolution of ¯uoropolymers, based on these last 65 years, enables one to understand
their extraordinary development and is presented in Table 1.
Fluorinated polymers are particularly interesting and attractive compounds because of their versatility
(they range as a wide scope of thermoplastics, elastomers, plastomers, thermoplastic elastomers and can be
semi crystalline or totally amorphous) and their unique combination of relevant properties [3] (mainly linked
to the low polarizability and the strong electronegativity of the ¯uorine atom, to its small Van Der Waals
Nomenclature
CSM Cure site monomer
CTFE Chlorotri¯uoroethylene
E Ethylene
HFP Hexa¯uoropropylene
HFPO Hexa¯uoropropylene oxide
IRFI a,v-Diiodoper¯uoroalkane
ITP Iodine transfer polymerization
M Monomer
NMR Nuclear magnetic resonance
P Propene
PAVE Per¯uoroalkyl vinyl ether
PAAVE Per¯uoroalkoxy alkyl vinyl ether
PFPE Per¯uoropolyether
PMVE Per¯uoromethyl vinyl ether
PPVE Per¯uoropropyl vinyl ether
PTFE Polytetra¯uoroethylene
PVDF Polyvinylidene ¯uoride
R Alkyl group
RF Per¯uorinated group
RFI Per¯uoroalkyl iodide
Sty Styrene
TAC Triallyl cyanurate
TAIC Triallyl isocyanurate
TFE Tetra¯uoroethylene
TFS a,b,b-Tri¯uorostyrene
Tdec Decomposition temperature
Tg Glass transition temperature
VDF (or VF2) Vinylidene ¯uoride (or 1,1-di¯uoroethylene)
D Heating
radius (1.32 AÊ ) and to the strong C±F bond (485 kJ mol 21). Hence, ¯uoroplastics with high ¯uorine contents
exhibit high thermal, chemical, ageing and weather resistance, excellent inertness to solvents, hydrocarbons,
acids and alkalies, low dielectric constants, low ¯ammability, low refractive index, low surface energy
(interesting oil and water repellency) and moisture absorption. Furthermore, the presence of the strong
C±F bond [3] has a crucial impact on the high resistance to oxidation and to hydrolytic stability.
Hence, these specialty polymers have been used in many applications: building industries (paints
and coatings resistant to UV and graf®ti), petrochemical and automotive industries, aerospace and
aeronautics (use of elastomers as seals, gaskets, O-rings used in extreme temperatures for tanks of liquid
hydrogen for space shuttles), chemical engineering (high-performance membranes), optics (core and
cladding of optical ®bers), treatment of textile, stone (expecially for old monuments), microelectronics.
In spite of their high price (mainly linked to unusual processes of polymerization, to the cost of purifying
Table 1
Historical development of ¯uorinated polymers
1st Generation: Fluorinated homopolymers
1934±1938 PCTFE (C2F3Cl), PTFE (C2F4)

1950 PVDF (C2H2F2), PVF (C2FH3), PTrFE (C2F3H)
2nd Generation: Fluorinated copolymers
1950±1960 VDF/CTFE (C2H2F2 ±C2F3Cl)

VDF/HFP (C2H2F2 ±C3F6)
FEP (C2F4 ±C3F6)
PFA (C2F4 ±CF2yCF±OC3F7)
1980 ETFE (C2H4 ±C2F4)
E/CTFE (C2H4 ±C2F3Cl)
Elastomers (see Table 2)
Copolymers of ¯uorinated acrylates
1989 Amorphous transparent copolymers: Cytop w and Te¯on w AF (then Hy¯on w AD, 1996)
3rd Generation: Fluorinated functional polymers
1980 Ion exchange membranes; room temperature crosslinkable paints

1995 Crosslinkable resins and elastomers
the gaseous monomers and to the small scale of production), these polymers have found major devel-
opments in modern technologies.
Various books [4±9], chapters of books [10] or reviews [11±14] have provided useful and exhaustive
data on homopolymers and are not detailed in this review.
However, ¯uoroplastics have various disadvantages: the homopolymers are often crystalline, exhibit a
poor solubility in common organic solvents and are not cured or crosslinked easily. This is why the
generation of ¯uorinated copolymers [15±26] (involving a mixture of comonomers that induces disorder
of the macromolecule and thus reduces or gets rid off the high crystallinity of the homopolymer) has
extensively grown without possessing the drawbacks of homopolymers mentioned above. After present-
ing various ¯uoroole®ns involved in copolymerization and reminding several theoretical laws and
concepts on the copolymerization, the objective of this review deals with the synthesis, characterization,
properties, curing and applications of numerous ¯uoroelastomers (including per¯uoroelastomers and
those containing heteroatoms).
2. Fluoroelastomers
2.1. Combination of ¯uoroalkenes
Table 2 lists various comonomers which constitute today's commercial elastomers. This table exhibits
lines associated to columns for which most intersections lead to ¯uoroelastomers [16±23]. The ¯uori-
nated comonomers can be chosen for speci®c properties of the co-, ter- or tetrapolymers. To obtain
110
Table 2
Main commercially available ¯uoroelastomers (CTFE Ð chlorotri¯uoroethylene (F2CyCFCl); HFP Ð hexa¯uoropropene (F2CyCFCF3); HPFP Ð 1-
B. AmeÂduri et al. / Prog. Polym. Sci. 26 (2001) 105±187

hydropenta¯uoropropene (HCFyCFCF3); P Ð propene (H2CyCHCH3); PMVE Ð per¯uoromethyl vinyl ether (F2CyCFOCF3); TFE Ð tetra¯uoroethylene
(F2CyCF2); VDF Ð vinylidene ¯uoride (or 1,1-di¯uoroethylene) (F2CyCH2); X Ð CSM (G is a halogen atom or a functional group) (F2CyCF±R±G))
HFP PMVE CTFE P HPFP
VDF Daiel w 801 (Daikin) ± Kel F w (Dyneon) ± Tecno¯on w SL (Ausimont)

Fluorel w (3M/Dyneon) SKF w-32 (Russia)
Tecno¯on w (Ausimont) Voltalef w (Elf Atochem)
SKF w-26 (Russia)
Viton w A (DuPont)
TFE ± Kalrez w (DuPont) ± A¯as w (Asahi Glass) ±
w w
VDF 1 TFE Daiel 901 (Daikin) Viton GLT (DuPont) ± ± Tecno¯on w T (Ausimont)
Fluorel w (Dyneon)
Tecno¯on w (Ausimont)
Viton w B (DuPont)
1 E: Tecno¯on w
(Ausimont)
1 X: Viton w GH (DuPont)
elastomeric properties (i.e. amorphous material with a low glass transition temperature), basic mono-
mers such as vinylidene ¯uoride or 1,1-di¯uoroethylene (VDF or VF2) and tetra¯uoroethylene (TFE)
(lines) can be copolymerized with other ¯uorinated co-monomers of topological similarity with some-
times a bulky group attached to a vinyl functionality [17,22±24]. One ef®cient example concerns the
introduction of hexa¯uoropropene (HFP) into highly crystalline PVDF to reduce the crystallinity and for
suf®cient incorporated HFP a totally amorphous rubbery polymer is obtained. If improved low-tempera-
ture ¯exibility is required, per¯uoroalkyl vinyl ethers (PAVEs) (and especially those containing more
than one oxygen atoms) are preferred over HFP. It is well-known that poly(hexa¯uoropropylene), PHFP
can be produced under ªexoticº conditions [4] (high pressure and temperature or special electron beam
irradiations). Except for VDF/hexa¯uoroisobutylene, CTFE/ethylene (E), CTVE/vinyl ethers, TFE/E
and TFE/propene which possess an alternating structure (see Section 3.2.3.), all other copolymers are
random. In several cases, another reactive monomer is added in small amount to provide functional
groups suitable for curing or crosslinking. This cure site monomer (CSM), which is more dif®cult to
prepare, is usually added in few mole percents (less than 5%).
Table 2 also supplies ¯uoroelastomers trademarks produced by main important companies involved in
¯uorine chemistry.
This review illustrates numerous examples of ¯uoropolymers and mainly those of TFE- and VDF-
based copolymers (Sections 4 and 5).
2.2. Synthesis of ¯uoroalkenes
This section focuses on the preparation of most known ¯uoroalkenes, while the more exotic ones are
detailed later: especially PAVEs or PAAVEs described in Section 4.5 or ¯uorinated nitroso or phos-
phazene monomers (reported in Section 6.3).
Fluoroalkenes [4,10,11,22] are obviously the raw materials for obtaining ¯uorinated cotelomers [27]
or ¯uoroelastomers.
2.2.1. Vinyl ¯uoride

Vinyl ¯uoride can be prepared either in a two-step process by the addition of two moles of HF onto
acetylene leading to 1,1-di¯uoroethane (CFC 152) which undergoes a dehydro¯uorination [28], or in a
one-step reaction catalyzed by mercury catalyst [29±31]:
Hg
HC CH + HF H2 C CHF
HF
CH3 CHF 2
CFC 152
This ole®n can also be obtained from the dehydrochlorination of 1-chloro-1-¯uoroethane [32] or 1-
chloro-2-¯uoroethane in vapor phase [33]. Other procedures have also been proposed [34].
2.2.2. Vinylidene ¯uoride (VDF or VF2)

Various syntheses are possible to prepare VDF.
First, the chlorination of CFC 152 to 1-chloro-1,1-di¯uoroethane (CFC 142) [35] followed by a
dehydrochlorination at about 700±9008C in the gas phase [36±39] is the most typical process:
CFC 152 + Cl2 CH3 CF2 Cl + HCl
H2 C=CF 2
The elimination can also be performed either at higher temperatures [36], in the presence of copper
catalyst [40] or at lower temperatures in the presence of steam.
Second, the hydro¯uorination of 1,1,1-trichloroethane yields CFC 142 [41] which is subsequently
dehydrochlorinated as above:
CH3 CCl3 1 HF ! CH3 CF2 Cl ! H2 CyCF2
D VDF
Third, the catalytic pyrolysis (at 4008C in the presence of CrF3´3H2O) of 1,1,1-tri¯uoroethane requires
speci®c conditions but produces VDF in high yield and purity [42±44].
Fourth, the dechlorinations of 1,2-dichloro-1,1-di¯uoroethane [45±47] and of other intermediates
[48]were also achieved:
Zn
ClCF2 CH2 Cl ! F2 CyCH2
In this review, Section 5 is devoted to copolymers from VDF.
2.2.3. Chlorotri¯uoroethylene (CTFE)

CTFE can be synthesized from the hydro¯uorination of perchloroethane leading to 1,1,2-trichloro-
1,2,2-tri¯uoroethane (CFC 113) subsequently dechlorinated in the presence of zinc/methanol [49±51] or
in the gas phase involving aluminum ¯uoride-nickel phosphate [52] or metal oxide catalysts in the
presence of hydrogen [53]:
Cl3 C±CCl3 1 HF ! Cl2 CF±CF2 Cl
CFC 113
Zn
CFC 113 ! F2 CyCFCl 1 ZnCl2
CH3 OH
2.2.4. Tetra¯ouroethylene (TFE) and hexa¯uoropropylene (HFP)

TFE can be produced from a non-catalytic gas-phase pyrolysis of chlorodi¯uoromethane (CFC 22) at
high temperatures (600±9008C) and atmospheric or subatmospheric pressures [37,54]. Steam or other
inert gas may be used as diluents. The reaction is assumed to occur via the formation and dimerization of
di¯uorocarbene and high yields (95%) are achieved:
2CHClF2 ! F2 CyCF2 1 2HCl
D
According to the reaction conditions (thermal pro®les of the pyrolyzer and temperatures) TFE can add
to di¯uorocarbene or decomposes itself.
Hence, major by-products, including HFP, highly toxic per¯uoroisobutylene (the lethal concentration
(LC 50) of which is only few parts per billion [55]), octa¯uorocyclobutane and also chloro¯uoroalkanes
are removed by a complex distillation [56,57].
HFP, obtained as a co-product in the production of TFE [58], is also prepared by heating TFE to 700±
9008C under reduced pressure [59±62]:
3F2 CyCF2 ! 2F3 C±CFyCF2
The relative amounts of TFE and HFP from the pyrolysis processes can be controlled by the reaction
conditions. HFP has also been prepared by pyrolysis of 2-chloro-1,1,1,3,3,3-hexa¯uoropropane [63].
Other syntheses of TFE and HFP have been reported already [54,64], but they are not practiced
commercially. The copolymers of TFE are described in Section 4.
While 2-hydropenta¯uoropropene is prepared by Ausimont [65] from HFP, tri¯uoroethylene is
prepared from 1,1,1,2-tetra¯uoroethane (CFC 134a), produced by various companies [66].
Regarding hazards and price, TFE, which may de¯agrate with considerable violence under pressure,
heat and in the presence of oxygen (the reaction is exothermic to the extent of 276 kJ mol 21) [65], as
tri¯uoroethylene [66], is according to certain companies at least 10 times more expensive than VDF.
2.2.5. 3,3,3-Tri¯uoropropene
As mentioned above, the preparation of such a monomer has been reported already in the patent
literature [67]. This ¯uoroole®n has been involved in the copolymerization of various other ¯uorinated
alkenes such as TFE [68±72] which will not be detailed in this review. However, it is an extremely
useful precursor of methyl(3,3,3-tri¯uoropropyl)dichlorosilane (by hydrosilylation reactions) for the
preparation of commercially available ¯uorosilicones as described in Section 6.5.
2.2.6. Fluorinated styrenic monomers

Fluorinated aromatic monomers are scarce and examples are given hereafter considering styrenic
monomers where the ¯uorine atoms are linked to the ethylenic carbon atom, only.
Regarding a,b,b-tri¯uorostyrene (TFS), various ways of synthesis have been proposed. A one-step
method consists in the addition of TFE to LiC5H6 leading to TFS [73]. Other routes start from tri¯uor-
oacetic acid ¯uoride either via a Friedel and Craft reaction [74] or via an organomagnesian [75], leading
to CF3C(O)C6H5 as a useful intermediate of TFS.
The organometallic approach was also suggested by Burton et al. [76,77] who isolated TFS in 74%
yield, as follows (X Cl or Br):
DMF Pd PPh3 4
F2 CyCFX 1 Zn ! F2 CyCFZnX ! F2 CyCFC6 H5
Although homopolymerization of such tri¯uorovinyl aromatic monomers is dif®cult, except in emul-
sion [78,79] or plasma [80] processes, the copolymerization with F2CyCFY (with Y Cl, F, CF3) was
successfully achieved leading to novel sources of energetic materials [81].
Poly-TFS possesses much better resistances to oxidation and to chemicals than those of halogenated
homologues. On the other hand, a wide range of functional groups can be attached to the aromatic ring. A
sulfonated polymer was successfully used as a membrane for fuel cells by General Electric Co. [75,79].
Other ¯uoroaromatic monomers are synthesized from the reaction of triphenylphosphorane with
chlorodi¯uoromethane, leading to F2CyCRPh (R H or CH3) [82].
2.3. Polymerization of ¯uoroalkenes
Direct radical co- or terpolymerization of ¯uoroalkenes has been further proved to be a versatile way
that offers many opportunities for obtaining a wide range of ¯uoropolymers.
Homopolymerization or copolymerization of ¯uoroole®ns have been described previously [8±
12,17±24,67], mainly from aqueous dispersion techniques (emulsion or suspension) or by solution
as processes. Random copolymers can be obtained by feeding into the autoclave one or a mixture of
comonomers. In the case of copolymerization, reaching a more constant composition of the copolymer
can be achieved by adjusting the composition of the monomers in the autoclave according to their
reactivity ratios (see Sections 4 and 5 and Tables 5 and 7 for copolymers involving TFE or VDF,
respectively).
As known earlier the (co)polymerization of ¯uoroole®ns is carried out in a radical way. Basically, this
reaction is composed of four main steps: initiation, propagation, transfer and termination, already
described in main text books or reviews.
Initiators can be commonly used, such as potassium or ammonium persulfates (emulsion process) or
peroxides (suspension and solution processes). Interestingly, the use of ¯uorinated telechelic peresters
[83±85], synthesized by the oxidation of ¯uorinated acid chlorides [83±85] or by the direct addition of
acid ¯uorides [86] to hydrogen peroxide, were successfully used by Rice and Sandberg in the copoly-
merization of VDF and HFP leading to original ¯uoroelastomers [83,87], as follows:
O O O
H 2 O2
F3 CCH2 O2 C(CF2 )3 CCl F3 CCH2 O2 C(CF2 )3 CO OC (CF2 )3 CO2 CH2 CF3
NaOH, H 2 O
VDF / HFP
F3 CCH2 O2 C(CF2 )3 (VDF) (HFP) (CF2 )3 CO2 CH2 CF 3
-5°C 0.65 0.35
n
The average molecular weight determined by vapor pressure osmometry (VPO) was ca. 4000.
More recently, hydrogen peroxide was used to prepare novel a,v-dihydroxylated poly(VDF-co-HFP)
in a two-step procedure [88] (G designates CH2OH or CO2H):
H2 O2 + n VDF + p HFP HO (VDF)x (HFP) G

y z
A
AlLiH4
A HO (VDF) (HFP) CH 2 OH
x y z
While propagation of monomers occurs in a classical way (although the propagation-rates of all
monomers have not yet been assessed even if various reactivity ratios have been determined already,
Tables 5 and 7), termination step proceeds by recombination, only.
Obviously, the use of chain transfer agent enables one to obtain lower molecular weights and,
according to the nature of this reactant, functional compounds can be obtained or a better control of
the copolymerization can be achieved [27,89]. According to the amount and of the transfer-ef®ciency of
such a reagent, conditions of telomerization [90±93] can be realized. Such a reaction represents a very
interesting model of polymerization since it leads to low-molecular weight polymers with well-de®ned
end-groups. A quasi-exhaustive list of chain transfer agents used in the telomerization of main ¯uor-
oalkenes was previously reported [27].
3. Copolymerization
3.1. Introduction
As mentioned in Section 1, ¯uorinated homopolymers are often crystalline and insoluble in common
organic solvents. However, as indicated in this review, the introduction of a comonomer enables the
resulting polymer to loose its crystallinity. Indeed, copolymerization is the most general and powerful
method to perform effective systematic changes in polymer properties, and is widely used in the
production of commercial polymers and in basic investigations of structure±properties relationships.
As a result, copolymerization modi®es the symmetry of the polymeric chain and modulates both
intramolecular and intermolecular forces, so that properties such as melting point, glass transition
temperature, crystallinity, stability, elasticity, permeability and chemical reactivity may be varied within
wide limits. Literature dealing with copolymerization is abundant in books [94] or reviews [95±99].
3.2. Various kinds of ¯uorinated copolymer
As shown in this review, most ¯uorinated copolymers are random. But, it has been found that block,
grafted or alternated ¯uorocopolymers have been synthesized already and few examples are supplied
below.
3.2.1. Fluorinated block copolymers

Several examples are given hereafter regarding block copolymers, although others are reported in
Sections 6.2 and 6.5.
Tatemoto et al. [100] prepared poly(VDF-co-HFP)-b-PVDF block copolymers by controlled (or
pseudo-living) iodine transfer polymerization [101±103] using an a,v-diiodoper¯uoroalkane (IRFI)
which generated a ®rst elastomeric block 1. This was then able to initiate the polymerization of VDF
(Fig. 1), as follows:
I R F I + a VDF+ b HFP I (VDF) (HFP) RF (VDF) (HFP) I
x y x y
z z
1
1 + c VDF I(VDF) (VDF) (HFP) R’ (VDF) I

n x y F m
2z
These special ¯uoropolymers, called thermoplastic elastomers, launched by the Daikin Company in
1984, under the Daiel w trademark, are composed of soft segments (containing the VDF/HFP blocks) and
hard ones composed of PVDF or E/TFE blocks [103].
In a similar process, various models of multiblock copolymers containing VDF, tri¯uoroethylene and
HFP were proposed from controlled step-wise (co)telomerization of ¯uoroole®ns [104].
On the other hand and involving the cleavage of the C±Br bond regarded as stronger than the C±I one,
two processes have been used to prepare di- or triblock copolymers. The ®rst one, as mentioned above,
lies on the controlled radical polymerization by bromine transfer [105] (called atom transfer radical
polymerization, ATRP) of styrene from a,v-dibrominated intermediates 2 regarded as ªmacroinitiatorsº
[106]. These dihalogenated compounds were prepared by telomerization of VDF with 1,2-dibromote-
tra¯uoroethane [107], as follows:
BrCF2CF2Br peroxide
+ n VDF Br RF (VDF)n Br
2 + p H2C = CH ATRP Br(Sty)x RF (VDF) n (Sty) y Br
The second process involving a C±Br cleavage was used by Moggi et al. [108] who telomerized VDF
with v-bromoper¯uorinated polyethers in a non-controlled process:
rad:
CF3 OC2 F4 m OCF2 p Br 1 nVDF ! poly fluoroether-b-PVDF
These above diblock copolymers exhibit a heterogeneous morphology with two amorphous zones
assigned to both blocks. That attributed to per¯uorinated polyether had a Tg of 21438C in all the cases,
while the second one depended upon the chain length of VDF blocks, hence varying from 282 to 2528C
for a number of VDF units ranging from 13 to 71.
A similar investigation leading to PFPE-b-poly(VDF-co-HFP), from the radical cotelomerization of
VDF and HFP with PFPE-I (where PFPE stands for per¯uoropolyether), is reported in Section 6.2.
Another example of synthesis [109] of diblock copolymers (4) also deals with the chlorine transfer
radical polymerization (via a CCl3 end-group) of various monomers (M) (styrene, MMA, methyl acry-
late and butyl acrylate) initiated by VDF telomers (3) with DPn ranging between 5 and 16:
rad:
Cl3 C±H 1 nVDF ! Cl3 C± VDFn ±H
3
CuCl;bipyrid:
3 1 pM ! PVDF-b-poly M
4
Interestingly, whatever the VDF telomer/M couple, the average molecular weight in number M n of 4
increased with the monomer conversion and experimental values where close to the theoretical ones. In
w =M
addition, narrow molecular weight distributions and low polydispersities M n , 1:2 were obtained
as evidence of a controlled radical polymerization.
Another attempt of synthesis of ¯uorinated diblock copolymers was recently achieved in our
laboratory by a controlled radical step-wise copolymerization involving Tempo as a counter radical
[110]. Its structure was the following:
CH3
H3 C C (Sty) (CH2 CH) O N
n p
CN
CH2 OC2 H4 C8 F17
The following example was suggested by Oestreich and Antonietti [111] who allowed poly(styrene)-
b-(polybutadiene) ªblock copolymersº (SB) containing 90% of 1,2-butadienic units in the polybutadiene
block (prepared by anionic polymerization) to be ¯uorinated via two two-step procedures from the
pendant double bonds of the butadienic block (leading to rather ªgraftedº segments). The ®rst method
consists in achieving a hydroboration in the presence of 9-bicyclononyl borane (9-BBN) followed by an
oxidation that generated hydroxy side groups. Esteri®cation of these functions with per¯uorinated
carboxylic acid chlorides introduced ¯uorinated side groups in the butadienic blocks. The second
route deals with the epoxidation of 1,2-double bonds in the presence of metachloroperbenzoõÈc acid
(MCPBA) followed by the opening of the oxirane by the same above ¯uoroacid chlorides. Both ways are
summarized in the following scheme, where one 1,2-pendant double bond of the butadiene block is
presented only (RF represents C7F15):
(Sty)p (CH2 CH) n

CH CH2
1. 9-BBN
- MCPBA
2. H2 O-2 /OH
(Sty)p (CH2 CH) (Sty)p (CH2 CH)n

n
C2 H4 OH O
RF COCl RF COCl
pyridine Bu4 N+ Cl -
(Sty)p (CH2 CH) n (Sty)p (CH2 CH) n

C2 H4 OCORF CHCl
CH2 OCORF
The last example chosen was proposed by De Simone and co-workers [112,113] who prepared
amphiphilic block copolymers by controlled radical polymerization either from benzyl N,N-diethyl
dithiocarbamate [112] (by heating in supercritical CO2 or under photoinitiation) or from brominated
agents [113] as follows:
CH2 SCN(Et)2 + H2C=C(CH3)CO2C2H4N(Et)2 ∆ or hυ CH2(M1)nSCN(Et)2

S M1 5 S
5 1 H2 CyCH±CO2 CH2 C7 F15 ! poly M1 -b-P FOA

FOA
By atom transfer radical polymerization, various poly(M1)-b-PFOMA were obtained, M representing

MMA, 2-hydroxyethyl methacrylate, styrene, tert-butyl acrylate, ethyl hexyl acrylate with average
molecular weights ranging from 40,000 to 56,000.
3.2.2. Fluorinated graft copolymers

Although various possibilities of ¯uorinated graft copolymers have been achieved [114,115], one of
the rare examples of elastomeric graft copolymers was discovered by the Central Glass Company which
produces Cefral Soft w. Its synthesis ®rst involves the terpolymerization of VDF and HFP with an ole®nic
peroxicarbonate. This last monomer was ®rst reactive with its double bond at low temperatures (508C)
leading to a ¯uorinated elastomer (7) bearing peroxicarbonate side groups, followed by a further step
that enabled the peroxicarbonate to initiate the polymerization of VDF yielding PVDF grafts, as follows
[116]:
O
K 2 S2 O 8
n VDF + m CTFE + pH2C=CHCH2 OCO OtBu (VDF)w (CTFE)x (CH2 (CH)y
50°C
CH2
O
C=O
O
OtBu
7
958C
7 1 qVDF ! poly VDF-co-CTFE-g-PVDF
3.2.3. Fluorinated alternating copolymers

As for alternating ¯uorinated copolymers, many examples have been provided in various reviews
[95,96,99,117±119] showing mainly that alternating copolymerization occurs between donor and accep-
tor monomers that have high positive or negative value of e parameter of the Alfrey and Price [120] Q±e
scheme (see Section 3.3.5). As ¯uorinated alkenes are electron-withdrawing ole®ns, they are intent on
reacting easily with donating monomers such as vinyl ethers. The best example lies on the CTFE/vinyl
ether couple which has already led to industrial Lumi¯on w (Asahi Glass), Fluorobase w (Central Glass),
Zef¯e w (Daikin), Fluonate w (Dainippon Ink) or DX 2000 w (Elf Atochem) products as ef®cient anti-
aging coatings.
In the same way, TFE/propylene [121] copolymers are alternating, produced by the Asahi Company
(and called A¯as w), and is going to be extensively described in Section 4.2.
Other industrial copolymers also result from such ªacceptor±donorº copolymerization. These are
Halar w (E/CTFE) or Tefzel w (E/TFE) produced by Ausimont or Dupont, respectively. These two
¯uorinated copolymers are thermoplastic in contrast to elastomeric A¯as w.
Although VDF does not react with vinyl ethers as CTFE, 1,1-dichlorodi¯uoroethylene, per¯uoroa-
crylonitrile, TFE or methyl per¯uoroacrylate (MPFA) do, it is able to produce, with hexa¯uoroisobu-
tylene, alternating thermoplastic copolymers commercialized by Allied under the CMX w trademark
[122±124]. However, various examples of couples of ¯uoroole®ns/non-¯uorinated monomers leading to
alternating copolymers are listed in Table 3 and their physical properties have been investigated: some of
them are crystalline while others exhibit elastomeric behaviors.
3.3. Kinetics of copolymerization
The copolymerization of two monomers M1 and M2 results in the formation of copolymers having
compositions and monomer unit sequence distributions which depend on the relative concentrations of a
variety of species and on their relative reactivities towards each other. Depending on the species
considered to be important, a number of copolymerization models have been proposed [95,96]. Most
of them are reminded hereafter.
3.3.1. Terminal model

In the simplest case (restricting all subsequent discussion to free-radical initiated processes), only the
relative rates of addition of M1 and M2 monomers to growing polymeric radicals need to be considered.
This situation, called ªideal copolymerizationº requires two propagation rates and can be characterized
by a single reactivity ratio r.
k1
M1 + M1 M1 M1
k2
M2 + M2 M2 M2
where r k1 =k2
Ideal copolymerization produces copolymers with Bernouillian monomer unit sequence distribution
[95,96].
The terminal model for copolymerization is the most used [145,146]. It involves the four propagation
Table 3
Examples of ¯uorinated alternating copolymers
Monomer a Comonomer b Properties c References
CTFE E Cryst. [125]

CTFE P ± [126]
CTFE IB Cryst. [127]
CTFE NVP Cryst. [128]
CTFE VAc ± [129]
CTFE VE Tg # 208C [117,130,131]
F2CyCCl2 VE ± [132]
F2CyCFCN a-ole®n d ± [133]
F2CyCFCN VE d ± [134]
HFIB VAc Tg 508C [135]
HFIB VDF Cryst. [122±124]
MPFA E ± [136]
MPFA Pd Rubber [137]
MPFA VAc ± [138]
MPFA VE d ± [134]
TFE E Cryst. [139]
TFE Pd Tg 0±58C [121,140]
TFE IB Cryst. [141]
TFE VAc ± [142]
TFE VE d Tg , 2108C [143]
a-F acrylonitrile 1,3-chd ± [144]
a
CTFE: chlorotri¯uoroethylene; HFIB: hexa¯uoroisobutylene; MPFA: methyl per¯uoroacrylate; TFE: tetra¯uoroethylene.
b
IB: isobutylene; NVP: N-vinyl pyrrolidone; VAc: vinyl acetate; VE: vinyl ether; VDF: vinylidene ¯uoride; 1,3-chd: 1,3-
cyclohexadiene.
c
Cryst.: crystalline; Tg: glass transition temperature.
d
Initiation under g-irradiation.
steps, macroradicals and M1 and M2 monomers. The four equations can be written as follows:
k11
M1 + M1 M1 M1
k12
M1 + M2 M1 M2
k21
M2 + M1 M2 M1
k22
M2 + M2 M2 M2
where kij represents the rate constant of addition of macroradical Miz onto Mj.
Copolymerization obeying to the terminal model produces copolymers with monomeric unit sequence
distributions that can be described from the ®rst order statistics of Markov [96,97].
At least, 90% of known copolymerization systems can be represented adequately by the ideal or
terminal copolymerization models, but copolymerizations involving polar monomers or monomers with
large steric requirements often need more complicated ones [97,98].
From writing differential equations which correspond to the rate of disappearance of monomers M1
and M2, and from assuming steady-state concentrations of the radical centers M1z and M2z a more simple
equation can be obtained, relating the ratio of monomers in the copolymer (d[M1]/d[M2]) to the concen-
trations of monomers in the feed ([M1] and [M2]):
dM1 M1 r1 M1 1 M2

dM2 M2 M1 1 r2 M2
the parameters r1 (or r12) and r2 (or r21) are regarded as reactivity ratios de®ned as follows:
r1 k11 =k12 and r2 k22 =k21
In 1965, Tidwell and Mortimer [147] proposed to classify methods of experimental determination of
reactivity ratios r1 and r2 in copolymerization from the Mayo and Lewis' differential equation [145], as
follows:
f1 r1 2 1 1 1
F1 f1 1
f12 r1 1 r2 2 2 1 2f1 1 2 r2 1 r2
where F1 and f1 represent the molar fractions of monomer 1 in the copolymer and in feed, respectively.
Tidwell and Mortimer distinguished ®ve groups of methods summarized below:
(a) Approximative methods. The methods proposed by Kuo and Chen [148], Bauduin and Meghabar
[149], Kennedy and Lo [150] lead to approximative values of ri and are not able to supply any interval of
con®dence on these values. However, they may give useful data to choose the most adapted experiments
to assess the reactivity ratios from other ways.
(b) Curve ®tting methods. These methods consist in ®nding the r1 and r2 which lead to the polymer±
monomer composition curve that ®ts with the experimental data. Alfrey et al. [151] and later Braun et al.
[152] also suggested similar methods, the latter authors considering that experimental results for which
f1 , 0:5 are more representative of r2 while the others are more directed towards r1. Although such
methods assess r1 and r2 values in more accurate ways than that above, no interval of con®dence can be
supplied.
(c) Curve crossing method. Historically, that method is the oldest one and was proposed by Mayo and
Lewis [145].
Then, Joshi and Joshi [153] suggested more accurate solutions for which an interval of con®dence on
the ri values can be assessed.
(d) Methods by linearization. Linearization methods are based on mathematical changes of Eq. (1)
where r1 and r2 reactivity ratios appear in the coef®cients of linear equations, the variables being
functions of f1 and F1 experimental values.
The most known and the oldest method was proposed by Fineman and Ross [154] and was improved
by Tosi [155], then by Yezreliev et al. [156] and also by Kelen and Tudos [157].
Non-linear regression method by the least square method. This method has been initially proposed by
Behnken [158], as a modi®cation or extension of the method by adjustment of curve. This method, also
detailed in Tidwell and Mortimer's review [147], indicates how the surface in which all the couples
composed of r1 and r2 values are located with a chosen probability (regarded as the domain of con®-
dence) can be drawn in the (r1, r2) plane.
3.3.2. Penultimate model

Merz et al. [159] proposed the penultimate model, reviewed by Tirrell [96]. Indeed, the propagation
step should take into account four distinct active enters, which are de®ned by the identities of their
terminal and penultimate units, given by eight equations, as follows:
k111
M1 M1 + M1 M1 M1 M1
k112
M1 M1 + M2 M1 M1 M2
k121
M1 M2 + M1 M1 M2 M1
k122
M1 M2 + M2 M1 M2 M2
k211
M2 M1 + M1 M2 M1 M1
k212
M2 M1 + M2 M2 M1 M2
k221
M2 M2 + M1 M2 M2 M1
k 222
M2 M 2 + M 2 M2 M 2 M 2
Hence, the copolymer composition determined by the relative rates of the monomer consumption is
becoming more complex [96].
The prediction of monomer sequence length by the penultimate model is conceptually identical to that
described for the terminal model. The probability (PBAA) that a MBM A chain end adds MA is:
MA
PBAA
MA 1 MB =rBA
Thus, the knowledge of the copolymerization reactivity ratio allows calculation of copolymer compo-
sitions and sequences as functions of the ratio of monomer concentration in the feed.
3.3.3. Complex participation model in the acceptor donor copolymerization

Radical copolymerization of electron rich alkenes (called ªdonor monomersº) with electron poor
ole®ns (case of ¯uoroalkenes, called ªacceptor monomersº) offer alternating copolymers over the entire
range of the feed composition [160], called AD copolymerization.
In such systems, one often observes a marked sensitivity of the overall copolymerization rate to
temperature, solvent and monomer concentrations [161]. However, Butler et al. [162] have also noted
anomalies in the stereochemistry and regiochemistry [163] of certain systems.
A mechanistic scheme that accounts for this behavior involves the participation of 1:1 alkenic electron
[DA] complexes in the propagation step. It is proposed that the 1:1 complex competes with free
monomers for the growing chain end. Modi®cation of the terminal model in this way requires consid-
eration of eight propagation steps well summarized by Tirrell [96].
It is well known that there are two major theories concerning AD copolymerization. Scheme 1
represents the copolymerization occurring either via the propagation of a complex (1) [164] or via
the propagation by free monomers (2) [165].
A + D DA complex
(2) (1)
A D
n
Scheme 1.
Both these mechanisms are controversial even with classical monomers usually involved in copoly-
merization (e.g. maleimides, vinyl ethers).
Matsuda et al. [166] performed a very interesting study on the terpolymerization of methyl tri¯uor-
oacrylate with TFE and E, considering that E only is able to copolymerize with both ¯uoromonomers
and they investigated both kinetics taking into account these two mechanisms: that from free monomers
and that involving the charge transfer complex (CTC) assuming that both complexes also copolymerize.
The authors observed that the experimental values were closer to the model proposed from the complex
than from the free monomer mechanism.
The CTC can be evidenced by several spectroscopic techniques such as UV [167] or 19F nuclear
magnetic resonance (NMR) [131]. Usually, the constant of this CTC is ranging between 0.05 and
1.00 l mol 21 at 208C.
3.3.4. Other copolymerization models

Two additional models Ð the complex dissociation [168,169] model and the depropagation model
[170] (which may occur at a temperature close to the ceiling temperature) Ð have not been considered
as extensively as the models above, but each of them is physically plausible and each has been analyzed
in suf®cient detail so that compositions and sequences may be calculated [96].
The excellent review of Tirrell [96] also details the evaluation of the copolymerization models
(composition and sequence, measurements of absolute rate constants) and the reader is directed to it
for a better description.
3.3.5. Q and e parameters and other concepts

Alfrey and Price [120] suggested two parameters assigned to each monomer involved in copolymer-
ization: these are the Q and e factors. Q is devoted to the resonance effect or stabilization and to the life
time of the radical formed (having a crucial in¯uence on the reactivity of the monomer) while e denotes
the permanent electric charge carried by the entity (radical or molecule).
The Alfrey and Price equation leads to the determination of Q and e from the reactivity ratios [171] by
both the following equations:
Q1
r12 exp2e1 e1 2 e2
Q2
Q2
r21 exp2e2 e2 2 e1
Q1
This Alfrey and Price Q±e scheme is useful for the interpretation of radical and monomer reactivities
and for the prediction of the monomer reactivity ratios in radical copolymerization. This remains the
most used model.
Table 4
e and Q values of ¯uorinated monomers
Monomer e Q References
H2CyCHCF3 0.42 0.130 [174]

H2CyC(CF3)OAc 1.51 0.069 [175]
H2CyCFC6H5 20.70 0.900 [176]
22.04 2.49 [177]
H2CyCFCONH2 1.45 0.540 [178]
H2CyC(CF3)CO2CH3 2.90 0.800 [179]
2.50 0.740 [180]
H2CyC(CF3)C6H5 0.40 0.780 [172,173]
0.90 0.430 [181]
HFCyCH2 0.60 0.250 [182]
0.72 0.008 [171,174]
1.28 0.012 [171]
20.05 0.016 [183]
20.80 0.010 [184]
H2CyCFCF2ORF 0.75 0.030 [185]
F2CyCH2 0.50 0.015 [173]
0.40 0.008 [183]
1.20 0.036 [186]
F2CyCCl2 2.10 0.041 [171]
CF3CFyCFH (cis) 2.10 0.002 [184]
F2CyCFH 1.15 0.009 [183]
F2CyCHCF3 0.31 0.002 [187]
F2CyCFCH2OH 1.52 0.011 [188]
F2CyCFC3H6OH 1.04 0.008 [188]
F2CyCFC3H6OAc 1.14 0.060 [189]
F2CyCFC3H6SAc 1.68 0.045 [190]
F2CyCFCl 1.84 0.031 [183]
1.56 0.026 [172±174]
1.48 0.020 [171]
F2CyC(CF3)COF 2.35 0.011 [186]
F2CyCFCO2CH3 2.37 0.035 [137]
1.20 0.048 [172±174]
1.5±2.1 0.01±0.20 [191]
2.2±2.6 0.04±0.06 [138]
F2CyCFOCF3 3.01 0.250 [192]
F2CyCFOC3F7 2.48 0.031 [192]
F2CyCFO(HFP)OC3F7 1.37 0.004 [193]
F2CyCFO±RF ±CO2R 1.08 0.006 [194]
F2CyCFO±RF ±SO2F 2.26 0.047 [192]
F2CyCFCF3 4.09 0.047 [174]
1.50 0.005 [195]
F2CyCF2 1.22 0.049 [191]
1.63 0.032 [172,196]
1.84 0.031 [183]
H2CyCFCHyCH2 20.42 2.100 [171]
0.63 1.880 [174]
F2CyCF±CFyCF2 0.58 0.820 [174]
Table 4 (continued)
Monomer e Q References
F2CyCF±CFyCF2 (cont.) 4.09 0.047 [183]

0.47 0.930 [197]
F2CyCF±C6H5 0.95 0.380 [171]
Compilations of Q and e values have been published by various authors, the most recent ones being
Refs. [172,173], both by Greenley. However, few values of ¯uoromonomers have been reported in these
compilations and we ®nd it interesting to supply a more exhaustive list (Table 4).
The general tendency shows that the more ¯uorine atoms onto the double bond, the higher the e value.
In most cases, Q values are very small except for those of styrenic and acrylic monomers. It is, however,
dif®cult to rationalize these values since various processes, methods of initiation, temperatures, solvents
and different ways to determine the corresponding reactivity ratios have been used. The low Q values are
good evidences of the poor ability of a ¯uorine atom for resonance stabilization of the radical on the
adjacent carbon atom.
In addition to the Q and e values of ¯uoroole®ns, the literature also quotes such parameters for
¯uorinated (meth)acrylates [136,171,198±205] (e.g. the ¯uorinated group is located in the b or g
position about the ester function), styrenics [171,177,206], maleimides [207,208] or fumarates [209]
which are not detailed in this review.
As several authors underlined, the Q±e scheme is probably too simpli®ed to discuss the reactivity of a
monomer in free radical reactions based only on separate resonance and polarity factors [210±213].
This is why other concepts have been proposed, e.g. by Jenkins.
The ªPatterns of reactivityº scheme, originally proposed in 1959, seems to provide a more accurate
prediction of monomer reactivity ratios than the Q±e scheme does.
4. Fluoroelastomers from TFE
4.1. Introduction
Polytetra¯uoroethylene (PTFE) is one of the most attractive ¯uoropolymers, thanks to its outstanding
properties of thermal stability, inertness and low surface tension. Most copolymers containing TFE are melt
processable [56,214] evidenced by, for example, those containing up to 6 mol% of HFP, PMVE or
per¯uoropropylether, (FEP w, MFA w or PFA w, respectively). They have high melting points of 265,
285 or 3058C, respectively.
However, FEP w polymers [56] do not have the same thermostability as that of PTFE and this enabled
TFE/PAVE copolymers to ®nd useful development [17±24,215]. Indeed, these latter ones possess heat
stability and high-temperature properties close to that of PTFE, and can be used at the same continuous
service.
Although TFE copolymerizes easily with E to produce an alternating highly crystalline copolymer
(Tefzel w from DuPont), it also copolymerizes with propylene leading to an alternating elastomeric
material (A¯as w from Asahi).
Besides these melt processable TFE-based copolymers, ¯uorocarbon elastomers containing TFE have
also been produced. For example those having both VDF and HFP have been of considerable commer-
cial interest since the 1950s [216,217]. They are described in the following sections (see Section 5.3).
Due to the shielding of the polymer backbone by the ¯uorine atoms, these elastomers exhibit far superior
chemical resistance and thermal stability over their hydrocarbon analogues. In spite of their extreme
inertness towards many chemicals, these polymers are readily attacked by bases and can easily be
dehydro¯uorinated. Besides, both diamine or diphenol-base cure systems generate a lot of unsaturations
in the polymer backbone, which are proned to nucleophilic attack by many additives (e.g. amines,
succinimides) that are used in engine oils.
To avoid the presence of base-sensitive sites in VDF/HFP elastomers, two different ways are possible:
to prepare ¯uorocarbon elastomers without any HFP or to synthesize ¯uorocarbon elastomers without
any VDF [218,219].
The ®rst group encompasses copolymers of TFE/P, VDF/TFE/P or VDF/TFE/PMVE [15±
24,89,220,221]. The second group comprises elastomers based on TFE with PAVEs: TFE/PAVE,
TFE/PAVE/ole®n [15±24,221,222].
In all these ¯uorocarbon elastomers, the main monomer is TFE.
4.2. Fluoroelastomers from TFE and propylene
In the early 1960s it was found that TFE readily copolymerizes with propylene (P) to give ¯uoroe-
lastomers, commercialized by the Asahi Glass Company as A¯as w elastomers [17±22]. This rubber
contains 54±57 mol% of ¯uorine, less than VDF/HFP (see Section 5.3) and other TFE-based ¯uoroe-
lastomers.
These copolymers have been prepared by emulsion polymerization with per¯uorocarbon surfactants
and a modi®ed persulfate redox system as the initiator [223±224]. The redox system consists of ammo-
nium persulfate, ferrous sulfate, ethylene diaminotetraacetic acid and sodium hydroxymethane sul®nate,
and the copolymerization was performed at a temperature range of 0±508C. The molecular weight of
copolymers obtained is rather high (higher than 1.5 £ 10 5) and the vulcanizates have good physical
properties [225]. At higher temperatures, other redox systems can be used but chain transfer reactions
start to dominate and, consequently, lower molecular weight polymers are produced [226,227].
A polymerization recipe containing water-soluble peroxydisulphates, thiosulphates or sulphites,
ferrous salts, pyrophosphate and ammonium per¯uorooctanoate is also employed in the temperature
range of 0±508C [228,229].
A new initiating system, containing tert-butyl peroxybenzoate and redox catalyst has also been used
successfully to copolymerize TFE with P in bulk [230] and emulsion [231±233] processes. It was found
that it exceeds considerable catalytic activity at low temperatures, increasing the alternating character of
copolymers obtained with improved thermal and chemical resistances [234].
The copolymerization of P and TFE initiated by g-radiations (from 60Co) or electron beams led to
elastomers with an alternating structure [234±238]. In the wide range of monomer compositions, (30±
90 mol% of TFE) the alternating copolymers were obtained and the TFE content in the monomer feed
affected the copolymerization rate and molecular weight of the copolymers. The reactivity ratios were
found to be rP 0:10 and rTFE 0:01 [236].
The copolymers can be crosslinked by high-energy radiations at room temperature [239], a reaction
accompanied by a HF-release.
Radiation-induced emulsion copolymerization of TFE with P has been studied extensively by

Matsuda et al. [240±244]. The rate of polymerization is proportional to the dose rate (0.3±
5.3) £ 10 5 R/h of 60Co source but the molecular weight of the copolymer does not depend on the
dose rate [245].
In the presence of oxygen, the radiation polymerization was accompanied by HF evolution [242,246]
from TFE oxidation followed by the hydrolysis of COF2. By increasing the surfactant concentration, the
rate of radiation polymerization increases and the molecular weight of the copolymer increases with the
temperature.
TFE/P polymers are usually cured by a peroxide coagent (radical trap). The system and radiation are
discussed more precisely in Section 7. To improve the curability, a third comonomer (CSM) has also
been included into the chain. TFE/P ¯uoroelastomers with small amount of CSM have also been
reported by various authors. Kojima et al. [247] have shown that a CSM such as glycidyl vinyl ether
may be introduced in the polymer without disturbing the predominant alternating structure of the
copolymer. These TFE/P/glycidyl vinyl ether terpolymers can be cured at room temperature with
tris(dimethylaminomethyl) phenol in the presence of phenol accelerators or at 1708C by diamines.
The same researchers [248] reported TFE/P/VDF terpolymers as a means of improving the low-tempera-
ture properties.
Different CSMs such as carboxylic [248], hydroxy [249], ester type monomers [249] or containing a
chlorine [248] terminal atom can be incorporated in the elastomeric macromolecules without upsetting
the alternating structure of TFE/P units.
A series of investigations by incorporation of a third comonomer with symmetric or pendant lateral
groups to TFE/P binary copolymers to decrease the glass transition temperature and the low-temperature
resilience has also been achieved [250±253]. The best results with improved thermal stability and Tgs
lower than 2208C were obtained by TFE/P/per¯uoropropyl vinyl ether (PPVE) terpolymers [253].
A¯as w TFE/P elastomers are endowed with interesting properties. They are resistant to H2S, oil and
gas, amine corrosion inhibitors, acid used in acidifying operations, steam/hot water/brine and CO2 and
methane gases [21]. TFE/P elastomers are replacing other elastomers in oil ®eld applications because of their
resistance to the wide range of chemicals, heat and pressures that can be encountered in these applications.
Polymers based on TFE, P and VDF show improved low-temperature properties, but give up some
chemical resistance and resistance towards polar solvents [254,255]. An interesting comparison of
elastomeric properties between such terpolymers and VDF/TFE/HFP was achieved by Grooteart et al.
[256]. They showed that these latter ones were much more base-sensitive than the former ones.
Prereacted bisphenol curatives have been used in TFE/P/VDF terpolymers [257].
4.3. TFE-based ¯uoroelastomers containing ethylene (E)
As mentioned in Section 4.1, TFE/E copolymers are crystalline and alternating, developed by DuPont
under the Tefzel w trademark.
Fluoroelastomers based on TFE, PMVE and E were also introduced by the DuPont Company in 1986.
The peroxide curing was possible by incorporation of bromine-containing CSMs [219]. The elastomers
have better low-temperature properties than TFE/PMVE and TFE/P and are suitable for long-time
service in hostile environments.
Copolymerization of PAVE such as CF2yCFO(CF2)3OC3F7 and E was carried out in emulsion and
yielded elastomers having an alternating structure (E/PAVE molar ratio of 53/47) with improved
low-temperature properties Tg 2428C [258]. When PAVE was partially replaced by per¯uoropro-
pylvinyl ether or VDF, terpolymers of higher Tg Tg 2278C were formed and another type of
¯uoroelastomers, comprising ole®ns with per¯uorinated monomers were developed (such as A¯as w
200 with 59% ¯uorine (developed by Asahi Glass)).
To reduce the regularity of HFP/VDF/HFP triads, which are base-sensitive sites, Arcella et al.
[89,220] introduced hydrogenated ole®ns (mainly E) as suitable protecting monomers. In this case, the
monomer sequence, e.g. HFP/VDF/HFP/E (regarded as the most probable) is a less base-sensitive material.
The polymerization reaction was carried out with a monomer mixture of VDF, HFP, TFE and E. To
overcome the low reaction kinetics and to obtain a low-molecular weight product, a special ªmicro-
emulsionº polymerization technique was involved. A ®rst product developed by this method in an
industrial scale is the Techno¯on w BRX 915N of Ausimont. A bromoper¯uoroalkyl vinyl ether CSM
was used to afford peroxide curability [259,260].
However, these ¯uoroelastomers still contain a non-negligible amount of hydrogen that renders them
more vulnerable to chemical and oxidative attacks than PTFE does. Nevertheless, DuPont's efforts have
led to ªelastomeric Te¯on wº thanks to Kalrez w per¯uoroelastomer composed of TFE and PMVE (see
Section 4.5). Such a polymer is resistant to hostile environments.
Hence, ¯uoroelastomers endowed with high resistance to polar solvents and to bases were synthesized
at Ausimont by Albano et al. [261] They copolymerized in emulsion TFE (33±75 mol%) with PVE,
mainly PMVE (15±45 mol%), 10±22 mol% of VDF, and optionally 0.05±2 mol% of a CSM (containing
iodine and/or bromine atoms present in the chain and/or in the terminal position). The reaction proceeds
in the presence of a microemulsion of per¯uoropolyoxyalkylenes and others. The terpolymer obtained is
vulcanized by peroxide with an excellent resistance to methyl tert-butylether and bases with a low
compression set properties.
4.4. Thermoplastic ¯uoroelastomers
Fluorinated thermoplastic elastomers (TPE) have been reported scarcely in most books dealing with
TPE [262,263].
Since the 1990s Daikin has introduced new ¯uorinated thermoplastic elastomers under the trade name
of Daiel w by applying their ªiodine transfer polymerizationº technology [100±103]. These copolymers
have triblock structure, B±A±B, where A is a ¯uorinated rubber and B is a ¯uorinated resin. Block
copolymers were obtained by a free-radical polymerization process of ¯uorinated monomers in the
presence of iodo-substituted ¯uorocarbons (see Section 3.2.1). In this case, the free radical polymeriza-
tion reaction behaves as a pseudo living or controlled polymerization, thus leading to continuous step-
wise chain growth. I(CF2)nI (n 4 or 6) is usually used as the diiodo reactant. In the ®rst stage iodine-
terminated TFE/VDF/HFP terpolymers were synthesized by emulsion polymerization. In the second
step the polymerization of the hard segment component takes place in the presence of the iodine-
terminated terpolymer emulsion. One type contains E/TFE/HFP (Daiel w T530), while the other one is
composed of PVDF blocks (Daiel w T-630) [264].
Recently, triblock ¯uorinated thermoplastic elastomers were synthesized using pseudo-living technology,
called ªbranching and pseudo-living approachº [265,266], starting from diiodinated compounds. However,
in this process, a small amount of a ¯uorinated diene was added leading to original ¯uoroelastomers, the
morphology of which was deeply modi®ed with improved mechanical and sealing properties [89].
4.5. Per¯uoroelastomers from TFE and PAVE monomers
The second group of ¯uoroelastomers without any VDF is based on TFE/PAVE or, to a less extent, on
TFE/PAVE/ole®n compositions.
Per¯uoroelastomers (mainly TFE/PAVE copolymers) offer the highest protection against high service
temperatures and oxidative environments by combining the resilience and sealing force of an elastomer
and the chemical inertness and thermal stability of PTFE [19]. These per¯uoroelastomers are similar to
Te¯on w PFA ¯uoropolymers as they have a fully ¯uorinated backbone but with 20±40 mol% vinyl ether
incorporated vs. 1±5 mol% of Te¯on w PFA. The latter, because of the lack of interpolymeric bonds and
ªcrosslinkingº sites, is a typical thermoplastic. Conversely, per¯uoroelastomers employ a crosslinking
network or a curing system, which provides the molecule with the combination of elastomeric behavior
and chemical resistance [221]. The commercially available per¯uoroelastomers are based on a copoly-
mer of TFE and PAVE. The most commonly used ether is per¯uoromethyl vinyl ether (PMVE), due to
its favorable polymerization properties, commercialized by DuPont under the trademark of Kalrez w. The
copolymerization of TFE with PMVE is readily initiated by free radicals in either ¯uorocarbon solvents
or aqueous emulsion systems [267]. The reactivity of both monomers towards radicals are suf®ciently
similar so that no dif®culty is experienced in obtaining homogeneous copolymers at high conversions of
monomers in systems producing polymers containing up to 50 mol% of the vinyl ether monomer. Higher
molecular weight PAVE may also produce elastomeric copolymers with TFE, however, at considerably
slower polymerization rates. A small amount (less than 5 mol%) of a third functional reactive monomer
(CSM) is added in the polymerization to create a crosslinking site on the polymer. The following
polymeric chain is ful®lled by using either redox or thermally generated free radicals.
(CF 2 CF 2 ) (CF 2 CF) (CF 2 CF) z

n m
O X
CF3
TFE PMVE CSM
This third monomer is usually added to make these polymer crosslinkable. It is required that this
monomer has the right functionality to enable the crosslinking reaction to take place. It is also important
that it copolymerizes with TFE and PAVE in a random fashion and causes no chain transfer reaction
[24]. The synthesis of the three classes of CSM that meet the above requirements is reported in Section 4
while the crosslinking is discussed in Section 7.
The most thermally stable per¯uoroelastomer available employs a nitrile-containing CSM. Per¯uor-
oelastomers containing bromine or iodine cure sites can be cured with peroxides in the presence of co-
agents and per¯uorophenoxy or hydrogen cure sites may be cured using stable bisphenols (Section 7).
Many patents have been deposited dealing with the use of different types of CSM improving the
properties of per¯uoroelastomers [268±274].
Aqueous emulsion polymerization systems, employing ammonium per¯uorooctanoate as the dispersing
agent and persulfate or the persulfate±bisul®te redox couple as the initiator, have been employed typically to
give high conversions of monomers in a few hours at temperatures ranging from 40 to 1008C and the pressure
within 5±7 Mpa and to lead to a product latex containing 25±30% of solid polymer [226,227,231±233]. The
polymer is isolated by coagulation either by freezing or adding an electrolyte to the emulsion (e.g. magne-
sium chloride or brine) followed by washings with water and with alcohol [232,233].
Aqueous suspension or dispersion methods result in increased occurrence of carboxylic acid end-
groups that are deleterious to the products during melt-processing steps and to the function of the
polymer. The reason is that PAVE undergoes a free-radical catalyzed rearrangement [67] shown
below (in the case of PPVE):
_
R_ F 1 CF2 yCFOC3 F7 ! RF CF2 CFOC 3 F7 a
_
RF CF2 CFOC _
3 F7 ! RF CF2 CFO 1 C3 F7 b
This reaction, if not controlled, would lead to unacceptably low-molecular weight copolymers.
Fortunately, the reaction is quite temperature dependent, so that the control of the polymerization
temperature in the range of 70±958C keeps the unimolecular transfer to a tolerable level [67]. The
second important modi®cation is the use of chain transfer agents. The solution process used for the
synthesis of TFE/PPVE copolymers employs CFC 113 as the solvent and per¯uoropropionyl peroxide
(3P) as the initiator at temperatures of 40±658C [270,275,276]. To control the molecular weight metha-
nol has been added as a suitable transfer agent.
Another possibility is to use supercritical CO2 as medium of the polymerization [277] of
¯uoroole®n. This process seems to avoid any formation of per¯uorinated acid ¯ouride and
hence leads to high molecular weights.
The ®rst per¯uoroelastomer grades were notably for setting new standards of thermal stability with
excellent resistance to almost all chemicals [19,22±24,222]. The second generation of per¯uoroelasto-
mers which has been developed in these last 15 years is Perlast w (from DuPont) [222]. It is a copolymer
of TFE with irregularly placed pendant per¯uorocarbon ether groups which are the key to promote both
low Tg (2198C) and low-temperature ¯exibility. The iodine-based cure system used with Perlast w is
unique and, while not affording the levels of extreme high-temperature resistance associated with the
triazine-cured Kalrez w 4079, the Perlast w system has the great advantage of not containing either metal
oxide or other metal-based catalysts.
Per¯uoroelastomers can handle the widest variety of chemical reagents of any elastomer available
today. In addition to the broad range of applications in the chemical processing industry they are used in
aircraft/aerospace, semiconductor chip manufacturing, chemical transportation, petrochemical indus-
tries, nuclear power plants and analytical and process instrumentation (see Section 11).
4.5.1. Synthesis of comonomers

Among per¯uorovinyl ethers two families can be distinguished. Those which are non-functional and
usually exhibit a per¯uorinated group [278] (such as PMVE, F2CyCFOCF3 or F2CyCFOCnF2n11,
n 2; 3) and those which bear an v-functionalized end-group such as sulfonyl ¯uoride, carboxy,
phosphonic acid, hydroxy, cyano, penta¯uorophenoxy or tri¯uorovinyl groups.
The synthesis of non-functional ones has been reviewed in the literature [4,5,8,9,13,279]
(starting from hexa¯uoropropylene oxide (HFPO)); that of several functional ones are described
hereafter.
The co- or ter- or tetrapolymers produced from them may fall into two classes: those acheived from
tri¯uorovinyloxy monomers bearing sulfonyl ¯uoride, carboxy, phosphonic acid functions leading to
membrane applications mainly; and those obtained from the other monomers mentioned above yielding
(per)¯uoroelastomers. Although the ®rst kind of copolymers are a bit far from the present topic, we
have found it interesting to recall them and hence to report brie¯y on the synthesis of the functional
monomers.
Functionalized per¯uorovinyl ethers have already reached an industrial production scale and three
main companies start their syntheses from TFE [279±284].
4.5.1.1. Sulfonic acid per¯uoroalkoxyvinyl monomers. In the DuPont and Dow Chemical technologies, a
¯uorinated sultone is a key reactant while the last step deals with a pyrolysis, as follows:
(a) DuPont technology. This sultone allows to introduce further a sulfonyl ¯uoride end-group and an
acid ¯uoride. The latter reacts to HFPO and, after pyrolysis leads to the sulfonyl ¯uoride per¯uorovinyl
ether, as follows:
SO3 CF2 CF2

CF2 CF2
O SO2
NR3
FOCCF2SO2F
CF2 CFCF3
O FOCCF (OCF2CF) OCF2CF2SO2F
n
CF3 CF3
∆
CF2 CF (OCF2CF) OCF2CF2SO2F
COF2 n
CF3
(n = 0,1)
(b) Dow chemical technology. This company uses chloropenta¯uoropropylene oxide (CPFPO) instead
of HFPO to promote the formation of F2CyCFO end-group more easily.
The radical copolymerization of this ¯uorinated sulfonyl ¯uoride monomer with TFE was success-
fully achieved [285].
(c) Asahi glass technology. The Asahi Glass company has two ways: ®rst, the electrochemical
¯uorination of a hydrogenated cyclic sulfone led to FOC(CF2)2SO2F (in high yields) which reacted
with HFPO and underwent a pyrolysis to yield F2CyCFO(CF2)3SO2F.
The second procedure generates a ¯uorinated thioether which is then oxidized as follows:
RSNa 1. Cl 2 /H2 O
CF2 CF2 HOOCCF2 CF2 SR 2. SOCl ClCOCF2 CF2 SO2 Cl
(CH3 O)2 CO 2
CF3
NaF HFPO
FCOCF2 CF2 SO2 F FCOCFOCF2 CF2 CF2 SO2 F
∆ CFOCF2 CF2 CF2 SO2 F

CF2
COF2
Other synthetic methods have been achieved on a research scale.

First, Krespan and England [286] synthesized per¯uoroallyl ¯uorosulfate from HFP and sulfur triox-
ide catalyzed by BF3 and then isolated F2CyCFCF2OC2F4SO2F according to the following process:
FSO2 CF2 COF 1 KF ! FSO2 CF2 CF2 OK ! FSO2 C2 F4 OCF2 CFyCF2
In addition, Kostov et al. [287] prepared FOCCF2SO2F (from the isomerization of the tetra¯uor-
oethane-b-sultone) that was reacted with F2CyCFCF2OSO2F (prepared from the addition of HFP onto
SO3, catalyzed by B(OCH3)3 as the catalytic complex) leading to F2CyCFCF2OC2F4SO2F. Nguyen and
Wakselman [288] used another way of synthesis and introduced various HFPO units.
More recently DesMarteau [289] achieved the synthesis of original F2CyCFOCF2CF(CF3)OC2F4 ±G
where G represents SO2NHSO2CF3, N(Na)SO2CF3 or N(Na)SO2C4F8SO2N(Na)SO2CF3.
In addition ¯uorinated monomers such as RF ±CFyCF±SO2F were also depicted [290].
4.5.1.2. Carboxylic per¯uoroalkoxyvinyl monomers. In contrast to the preparation of sulfonated per¯uor-

ovinyl ethers, the synthesis of carboxylated per¯uorovinyl ether is dif®cult.
The three companies above also share the market of these monomers.
For DuPont and Dow Chemical the difference is only in the di¯uorination step, as described below:
(a) DuPont technology. The reaction ®rst led to methyl-3-methoxy 2,2,3,3±tetra¯uoropropionate
(yield 74%) but the yield of the third step is low (8±15%). However, improvements were achieved
by the use of different aprotic solvents producing the per¯uoroacid ¯uoride in 30±40% [291].
CH3ONa SO3
CF2 CF2 CH3 OCF2 CF2 COOCH3 FCOCF2 COOCH3
(CH3O) 2CO
CF3 CF3
2HFPO
FCOCFOCF2 CFOCF2 CF2 COOCH3
CF3
∆
CF2 CFOCF2 CFOCF2 CF2 COOCH3
COF2
(b) Dow chemical technology. The ®rst two steps are similar to these above, but this company used
CPFPO instead of HFPO:
CH3 ONa SO 3
CF 2 CF 2 CH 3 OCF2 CF 2 COOCH3 FCOCF2 COOCH3
(CH3 O)2 CO
CF 2 Cl
CPFPO
FCOCFOCF2 CF 2 COOCH3
∆
CF 2 CFOCF2 CF 2 COOCH3
COFCl
(c) Asahi glass technology. Interestingly, for Asahi Glass, the telomerization of TFE with iodine
followed by a sulfonation brings an originality of synthesis, as follows:
I2
CF2 CF2 I(CF2 CF2 )2 I
CF2
SO3 /H2 SO4 F2 C CF2
O
O
CH3 OH
FOCCF2 CF2 CO2 CH3
CF2 CFCF 3
O (OCF2 CF) n O(CF2 )3 CO2 CH3
FOCCF
CF3 CF3
∆
CF2 CF (OCF2 CF) n O(CF2 )3 CO2 CH3
CF3 (n = 0,1)
Such a novel process enables this company to produce Flemion w membrane in an industrial scale
[279]. The cyclic lactone is obtained in high yields (70±80%) and the controlled addition of methanol to
the lactone generated 3-methoxycarbonyl per¯uoropropionyl ¯uoride selectively, to which HFPO was
added.
An alternative way from the lactone to the vinyl ether was proposed to improve the yield [279,292].
The addition of 1 mol of HFPO to the lactone occurred almost quantitatively and pyrolysis of the
asymmetric diacid ¯uoride led to the per¯uorovinyl ether in ca. 70% yield:
HFPO 1 D
lactone ! FOCC CF3 O CF2 3 COF ! F2 CyCFOC3 F6 CO2 CH3
2 CH3 OH
A research scale route involving an original ®nal step of deiodo¯uorination was described by Ukihashi
et al. [293], as follows:
TFE 2 IF
FOCC2 F4 CO2 CH3 ! IC2 F4 OC3 F6 CO2 CH3 ! F2 CyCFOC3 F6 CO2 CH3
KF=I2
4.5.1.3. Phosphonic acid per¯uoroalkoxyvinyl monomers. Besides most important carboxylic and sulfo-
nic groups novel per¯uorovinyl ethers bearing a v-phosphonic acid group were synthesized.
The ®rst one was achieved from the chemical change of carboxylic acid into phosphonic acid function
involving an iodinated intermediate as follows [293,294]:
1 Cl2
F2 CyCFOC3 F6 CO2 CH3 ! ClCF2 CFClOC3 F6 CO2 H
2 H2 O
I2 EtO2 P2 O
! ClCF2 CFClOC3 F6 I ! ClCF2 CFClOC3 F6 P O OEt2
2 CO2 tBuO2
Zn
! F2 CyCFOC3 F6 P O OEt2
EtOH
Then, the synthesis of dimethyl per¯uoro(3-vinyloxypropyl) phosphonate was achieved and co- or
terpolymerized with TFE and per¯uoro (propyl vinyl ether) [294].
Another alternative was proposed by Petersen et al. [295]; the iodides being converted into the
corresponding phosphonites using a photoreaction in the presence of tetraethyl pyrophosphite, followed
by an oxidation with hydrogen peroxide to prepare the desired diethyl phosphonate esters.
Other exotic functional per¯uorovinyl ethers were reported in the very interesting review published by
Ikihashi and Yamabe [281].
As a matter of fact, most applications [279±283] have been obtained from copolymers containing TFE
and per¯uorinated vinyl oxy-v-sulfonyl ¯uoride or v-carboxy (or derivatives): membranes for chlor-
ine±alkali electrolysis, per¯uorinated ion exchange materials, hydrogen±oxygen solid polymer electro-
lyte fuel cells or applications in space, ground (for vehicules) and undersea power sources.
4.5.1.4. Other functional PAVEs. They may contain other functional groups such as nitrile or hydroxyl
ones. Various ways of synthesis are reported below.
4.5.1.4.1. Nitrile-type. Many efforts have been made by Nottke [296] or Breazeale [297] who could
synthesize v-nitrile per¯uoro(vinyloxy) monomers. Two reaction schemes are presented below:
O CF3 O
RO2C(CF2)n C CsF
+ HFPO RO2C(CF2)n (HFPO)p CF C
F F
Na2CO3
RO2C(CF2)n O (HFPO)n CF=CF2
1) NH3
2) -H2O
N C (CF2)n O (HFP O)n CF=CF2
O O O CF3 O
C (CF2)3 C CsF
+ HFPO C(CF2)4OCF C
F F F F
KOH/CH3OH
O CF3 O
+ -
K OC(CF2)4OCF C
-
O K+
1)
2) CH3OH/H2SO4
O
CH3OC(CF2)4OCF=CF2
1) NH3
2) P2O5
N C(CF2)4OCF=CF2
Both these cyanoper¯uoro(vinyloxy) monomers were successfully co- or terpolymerized with TFE
and PMVE [296±301] or with VDF and PMVE [302] leading to crosslinked ¯uoroelastomers via
triazine rings (see Section 7.6) endowing them with outstanding thermal and oxidative stabilities [303].
To circumvent this additional curing, Watakabe et al. [304] ®rst synthesized an original
F2CyCFOC3F6CN (according to Sullivan's method [305] which was the ®rst reported way to prepare
v-cyano-per¯uoro(vinyloxy) monomers) that was further cyclized in two steps to produce a ¯uorinated
telechelic bis(tri¯uorovinyloxy)triazine.
4.5.1.4.2. Hydroxylated-type. Researchers at DuPont [284] succeeded in the preparation of v-hydroxy

Table 5
Reactivity ratios of TFE and monomers (E, propylene and mainly ¯uoroalkenes) in copolymerization
M rTFE rM References
H2CyCH2 0.10 0.15 [315]

H3CCHyCH2 0.06 1.00 [236]
F3C±CHyCH2 0.12 5.0 [71,316]
C3F7CHyCH2 0.21 2.3 [316,317]
FCHyCH2 0.06 0.30 [183]
tr-HFCyCHCF3 22 0.18 [316]
F2CyCH2 3.73 0.23 [318]
0.28 0.32 [183]
(F3C)2CyCH2 0.58 0.09 [316]
F2CyCHF 1.14 0.46 [183]
F3CCFyCH2 0.37 5.4 [316]
F2CyCFCl 0.75 1.04 [319]
0.80 1.10 [183]
1.0 1.0 [171]
F2CyCFBr 0.82 0.24 [319]
F2CyCFCH2OH 2.47 0.41 [188]
F2CyCFC3H6OH 1.57 0.45 [188]
F2CyCFCO2CH3 5.0 0.10 [320]
3.0 0.15 [191]
F2CyCFCF3 15 0 [321]
65 0 [183]
3.5 0 [322]
F2CyCFCF2ORFSO2F 10 0.3 [287]
F2CyCFOCF3 1.73 0.09 [193]
F2CyCFOC3F7 8.72 0.06 [193]
F2CyCFOCF2CF(CF3)OC3F7 15.60 0.02 [193]
F2CyCFO±RF ±CO2R 7.0 0.14 [194,323]
F2CyCFO±RF ±SO2F 8.0 0.08 [280,323]
per¯uorovinyl ethers such as F2CyCFOCF2CF(CF3)(O)(CF2)2CH2OH or F2CyCFOC3F6CH2OH by the

reduction, in the presence of sodium borohydride, of the corresponding methyl per¯uoro (i-oxa-i 1 1-
alkenoate) in high yields (86%), as follows:
NaBH4
F2 CyCFO±RF ±CO2 CH3 ! F2 CyCFO±RF ±CH2 OH
These v-hydroxyper¯uorovinyl ethers can also be functionalized into various original derivatives.
The ±OH end-group can be chemically changed into ±OR, where R represents CxCH, COC(CH3)yCH2,
CH2 ±C6H4 ±CHyCH2 [284].
4.5.1.5. Tri¯uorovinyl-type. The Asahi Company develops the very interesting per¯uoro-3-oxa-1,6-
heptadiene as an valuable intermediate which ring cyclizes to produce Cytop w as an amorphous per¯uor-
oplastic, combining high optical clarity and solubility with outstanding chemical, thermal and electrical
properties [279].
Almost similar ¯uorinated non-conjugated diene F2CyCFOCH2CF2CFyCF2 was prepared by Smart

et al. [306] in four steps (the last step deals with the dechlorination of ClCF2CFClCF2CH2OCFyCF2 in
the presence of zinc) and was easily homopolymerized and copolymerized with various ¯uoromono-
mers, the produced copolymers being useful in coatings and encapsulants.
On the other hand, the Ausimont Company also develops a soluble, transparent, ¯uorocyclic copo-
lymer containing TFE and ¯uorinated dioxolane under the Hy¯on w AD trademark [307].
4.5.1.6. Aryl tri¯uorovinyl ethers. Phenyl tri¯uorovinyl ether (PTVE) has been synthesized in a two-step
procedure: 3-phenoxy-2,2,3,3-tetra¯uoropropionic acid methyl ester was converted into its potassium
salt and pyrolyzed to yield PTVE [308].
Aryl tri¯uorovinyl ethers have been prepared usually by direct reaction of sodium areneoxides with
TFE [309] or by addition of arene oxides to 1,2-dibromotetra¯uoroethane yielding 2-bromotetra¯uor-
oethyl ethers, followed by elimination of ªBrFº in the presence of zinc [310]. In certain conditions, 1,3-
bis(¯uorovinyloxy) benzene was obtained.
Pattison [311] disclosed the synthesis of the following CSM:
F O (CFCF2O) CF=CF2 (where n = 1 or 2)

n
CF3
and could terpolymerize it with TFE and PMVE. Interestingly, the penta¯uorophenoxy side groups
were ef®ciently crosslinked [311] to promote ¯uoroelastomers with better mechanical properties [312].
Additional syntheses and molecules including aromatic a,v-bis(tri¯uorovinyl ethers) were summar-
ized in the chapter of Babb [313].
Other exotic functional per¯uorovinyl ethers were reported in the very interesting reviews published
by Yamabe et al. [281], Kirsh et al. [282] or Hung et al. [284].
4.5.1.7. Hydro¯uoroalkyl vinyl ethers. Few hydro¯uoroalkyl vinyl ethers F2CyCHORF have been
reported. To our knowledge, the Ausimont Company only has protected this invention [314] from the
dehydrochlorination of ClCF2CH2ORF.
For example, this company mentions the synthesis of various amorphous copolymers TFE/
F2CyCHOCF2CFHOC2F4OCF3 (mol% in the copolymer 79/21); TFE/F2CyCHOCF2CFHOCF3 (mol%
80/20) and TFE/F2CyCHOCF2CFHOC2F4O(CF2O)4CF3 (mol% 85/15) displaying Tgs of 224.7, 26.4
and 280.08C, respectively.
4.5.2. Copolymerization of TFE

Usually, most copolymers containing TFE are crystalline (melt processable copolymers are TFE/
PAVE as PFA w materials, TFE/HFP as FEP w or MFA w) while certain terpolymers are amorphous,
having elastomeric properties: besides TFE/P or TFE/PMVE, they contain VDF and HFP and are
developed in Section 5.
Regarding the kinetics of copolymerization, Table 5 displays the reactivity ratios of TFE and
comonomers. One of the most interesting works was investigated by Naberezhnykh et al. [183]
who suggested the decreasing reactivity series of various alkenes about a polymeric TFE chain as
follows:
H2 CyCH2 . H2 CyCHF . H2 CyCF2 . F2 CyCFCl . F2 CyCF2 . F2 CyCFH q F2 CyCFCF3
Hence, it can be deduced that the more the double bond is substituted by ¯uorine atoms, the more
reactive the TFE in copolymerization.
5. Fluoroelastomers from VDF (or VF2)
5.1. Introduction
Poly(vinylidene ¯uoride), PVDF or PVF2, is a thermoplastic that exhibits very interesting piezo-,
pyro- and ferroelectrical properties [325±328], is inert to various solvents, oils, acids and shows low
permeabilities to gases and liquids. Its Tg is about 2408C while its melting temperature varies from 158
to 1978C [329]. PVDF crystallizes in its called alpha form and can only give the beta form by stretching
at moderate temperature or when a certain amount of tri¯uoroethylene is added to it.
Homopolymers derived from VDF (or VF2) are long chain macromolecules endowed with a high
crystallinity rate rendering them unsuitable as elastomers. In contrast, copolymers of VDF with various
comonomers can fall into three categories: (i) when the amount of comonomers in the copolymer is as
small as that of VDF the resulting materials are thermoplastic with a lower crystallinity than that
mentioned above [25,26]; (ii) for a slightly higher content of comonomer thermoplastic elastomers
are obtained; (iii) for higher proportion of comonomers the produced copolymers are elastomeric,
amorphous with low intermolecular forces [17±24].
Moreover, although PVDF has found interesting applications, three major disadvantages are noted:
the high melting temperatures generate energetic costs for processing this polymer; the poor solubility in
common organic solvents (PVDF is soluble in DMF or dimethyl acetamide) and the dif®cult curing of
this material.
Hence, ¯uorocopolymers derived from VDF have drawn more interest. The ®rst copolymers of VDF
were patented as early as 1946 [330], followed by various generations of more and more VDF-based
copolymers. Tables 2 and 6 list various ¯uorinated elastomers and thermoplastics and show the great
versatility of compounds. In addition, the historical development of ¯uorinated copolymers from non-
¯uorinated monomers [25,26,118] or from ¯uoroole®ns [17,19,21±23,119] have been reported already.
A large variety of ¯uoroole®ns or functional comonomers can be successfully co-, ter- or tetrapoly-
merized and some examples are reported below.
Copolymers of VDF and CTFE or HFP represent the most important production, nowadays,
among the thermoplastic copolymers of VDF (those from vinyl ¯uoride [331] or TFE are also
thermoplastic, the latter ones being studied more due to their interesting ferroelectric behavior [332±
337]), while such a positive fate was reached for VDF/HFP elastomers produced by most ¯uoropolymer
industries.
As a matter of fact, four types of VDF-based ¯uoroelastomers are manufactured:
1. the earliest types of ¯uorocarbon elastomers are those prepared from VDF and HFP (type-A);
2. later, the B types were developed; they contain VDF, HFP and TFE base units;
3. ¯uoroelastomers designated as type-C were prepared to improve the solvent resistance; they contain a
higher ¯uorine content and CSM such as bromotri¯uoroethylene in addition to VDF, TFE and HFP;
4. the most recent ones are called type-D ¯uoroelastomers endowed with low-temperature resistance
and containing PAVE instead of HFP.
Table 6
Commercial copolymers of VDF: Thermoplastics (HFA Ð hexa¯uoroacetone)
Monomers Composition (mol%) Trade name Producer Melting point (8C)
VDF/CTFE 90/10 or 95/5 FORAFLON w Ato®na 165±167

90/10 or 95/5 KF POLYMER w Kureha ±
SOLEF w Solvay 150±165
VDF/TFE 80/20 KYNAR w SL, 7200 Ato®na N.A. 120
VDF/HFA 88/12 ± Central Glass 121
VDF/HFP 95/5 or 85/15 KYNARFLEX w Ato®na N.A. 135±160
SOLEF w Solvay 130±160
VDF/TFE/HFP 72/18/10 KYNAR w ADS Ato®na N.A. 90
VDF/TFE/HFP 30/55/15 HOSTAFLON w TFB Dyneon 160±185
(VDF/CTFE)-g-VDF (37.5/12.5)/50 CEFRAL SOFT w Central Glass 170
Regarding the behavior in solution of ¯uoroelastomers, little data is given in the literature [338,339] in
contrast to the Mark±Houwink relationships to determine molecular weights of PVDF [101,340,341].
To our knowledge, the most pertinent studies were achieved by Zinbo and Theodore [338] and by
Maccone et al. [339] who determined key molecular weight parameters by size exclusion chromato-
graphy, such as the average molecular weights and molecular weight distributions. The latter team
recently investigated on the branching of PVDF from the transfer to the polymer and then the cross-
linking in the presence of a ¯uorodiole®n [339].
5.2. VDF/CTFE copolymers
The ®rst copolymers of VDF/CTFE were produced for military interest from 1955 [342±346]. At this
time, these materials were the ®rst commercially available ¯uoroelastomers (called Kel w F) with vulca-
nizate properties higher to any of those existing.
Nowadays, according to the properties and applications required, various VDF/CTFE copolymers are
proposed: the amount of CTFE being crucial. Obviously, the elastomeric behavior is reached at 30±
50 mol% of CTFE while thermoplastic copolymers are obtained when containing less than 15 mol% of
CTFE [347] and are called ¯exible PVDF (Table 6).
In addition, a terpolymer of VDF, CTFE and a peroxide-functional allyl monomer has been synthe-
sized and subsequently grafted to PVDF to form a tough, ¯exible thermoplastic material, commercia-
lized by the Central Glass Company under the Cefral w trademark [116] (see Section 3.2.2).
VDF-based ¯uoroelastomers have outstanding resistance to ¯ame, chemicals, solvents, heat and
oxidation. These materials can be cured by bis-nucleophiles such as bisphenols or diamines or by
peroxides, as reported in Section 7.
5.3. VDF/HFP copolymers
The ®rst VDF/HFP copolymer was produced by DuPont de Nemours under Viton w trademark in 1957
with a better thermal stability and inertness to chemicals and a lower swelling to oils and petroleum than
those mentioned above [348].
In 1958, the 3M Company commercialized Fluorel w and, later, Ausimont and Daikin produced their
Techno¯on w and Dai-El w products, respectively.
VDF/HFP copolymers have also led to various kinds of product according to the content of HFP. As
above, at less than 15 mol% of HFP, the resulting copolymers show thermoplastic properties [349]
(Table 6), while those containing 30±40 mol% behave as elastomers [216,350±352]. Ajroldi et al. [353]
have demonstrated that a composition of 20±21 mol% HFP represents the best compromise between the
requirements of a low Tg and a fully amorphous elastomer.
Today, at least 25 grades are supplied depending on the nature of the comonomer, its content and its
distribution, molecular weights, state (powder or pellets) or presence of additives. Tables 2 and 6 list the
producers and tradenames of these copolymers.
On both academic and applied points of view, Apostolo et al. [354] recently performed interesting
investigations on the kinetics of emulsion copolymerization of VDF and HFP, monitoring all the
parameters of the experimental conditions and using an appropriate model.
Further original terpolymers based on VDF, HFP and TFE have also been produced [339,355,356].
For example, elastomeric terpolymers of VDF, TFE and HFP [217] provide gum stocks for high-
performance ¯uoroelastomers while for various amounts of these three ¯uoroole®ns, thermoplastic
elastomers can be produced, as reported by Hull et al. [356].
Indeed, according to the respective amounts of monomers, the elastomeric behavior [the region of the
triangle (the summits of which are VDF, HFP and TFE) encompasses a composition of 20±70% of VDF,
20±60% of HFP and 0±40% of TFE] [19] may fall into a thermoplastic elastomeric one (composition of
15±20 or 70±80% of VDF; 13±25 or 80±85% of HFP and 15±30 or 80±85% of TFE) as explained by
Logothetis [19] or Hull et al. [356].
For a structural point of view it is required that the microstructure of the elastomers contains about one
HFP unit for every two to four of the other monomer units to prevent any crystallization of the
terpolymer and to insure an amorphous macromolecule. This can be shown by 19F NMR as described
in various articles dealing with co- or terpolymerization [355,357,358] or with telomerization
[27,104,359±363]. Although no adjacent HFP units were found in the microstructure (its reactivity
ratio worth 0, Table 7), more recent telomerization of HFP gives evidence of the presence of two
consecutive HFP units when the reaction was carried out at higher temperatures [361±363] in the
presence of a,v-diiodoper¯uorobutane.
Regarding the thermal properties an interesting comparison of the Tgs of ¯uoroelastomers containing
VDF was realized by Van Cleeff [368] but showing that their Tgs could not be lower than 2298C.
5.4. VDF/penta¯uoropropene
Copolymers of VDF and 1-hydropenta¯uoropropene (CF3CFyCFH) have been produced by 3M [369]

or Montedison [370] to compete with those obtained from VDF and HFP, leading to original ¯uoroe-
lastomers, but their lower thermostability could not allow these materials to ®nd effective development.
Nevertheless, little basic research has been achieved [187], especially on the kinetics of copolymeriza-
tion that assessed the reactivity ratios of both comonomers (Table 7) showing that VDF is more reactive
than its penta¯uorinated partner.
Ter- or tetrapolymers containing 23±65% of VDF, 25±75% of F2CyCFORF, 0.3±0.5% of 2-hydro-
penta¯uoropropene and optionally, 0±30% of TFE were prepared by Bowers and Schmiegel [371].
These copolymers exhibit excellent low-temperature properties and processability when cured with
polyhydroxy compounds or amines.
5.5. VDF/TFE/propylene
As shown above, an HFP unit surrounded by two VDF units or by VDF and TFE units was shown to
be a useful structure curable by dinucleophiles [19,24,89], since the ±CF2CF(CF3)CH2CF2 ± may be
dehydro¯uorinated, leading to a reactive inner double bond.
This is why researchers at Asahi [372] substituted HFP by propene which enables the resulting
terpolymers to be resistant to dehydro¯uorination. Such a phenomenon is explained because CH3 is a
less electron-withdrawing group than CF3 and hence contributes to a lower acidity of the adjacent
methylene and methine functionality. As a result, this terpolymer has been crosslinked with dif®culty
in the presence of conventional nucleophilic cure systems [256,257,372].
5.6. VDF/tri¯uoroethylene and VDF/hexa¯uoroacetone copolymers
In contrast to the ¯uoropolymers mentioned above these copolymers are thermoplastics.

VDF can copolymerize in all proportions with tri¯uoroethylene (TrFE) [365] leading to random
crystalline copolymers. Nowadays, only VDF/TrFE copolymers containing a TrFE amount ranging
from 17 to 50 mol% have a slight commercial development limited to few tons per year. Although
expensive because of the price and hazards of TrFE, these copolymers have found applications in
various ®elds thanks to their piezo-, ferro- and pyroelectrical properties [373].
Copolymers of VDF with hexa¯uoroacetone [374±376] are crystalline and attractive for their elec-
trical properties.
5.7. VDF/PAVE
5.7.1. Copolymerization of VDF with non-functional PAVE

As indicated in Section 4, functional PAVE or per¯uoroalkoxy alkyl vinyl ethers (PAAVE) easily
copolymerize with TFE leading to novel materials useful for membrane applications. In contrast to these
copolymers which are not elastomeric, those obtained from the copolymerizations of PAVE (or
PAAVE) with VDF exhibit interesting elastomeric properties, although little development has been
achieved.
Indeed, the ether group brought by the PAVE (or PAAVE) comonomer allows the macromolecule to
exhibit a low glass transition temperature and in certain cases, elastomers resistant to low temperature
endowed with good thermal stability have been obtained.
First, Albin and Gallagher [377] from Du Pont, pioneered this research in the 1960s from an emulsion
process, yielding copolymers containing PMVE with a temperature of ¯exibility ranging from 228 to
2248C. This reaction evidences the poor reactivity of PMVE (rPMVE 0; rVDF 3:4; Table 7).
However, adding traces of TFE led to commercially available Viton w GLT (from DuPont) having
outstanding properties [23,378]. This terpolymer exhibits the following repeating unit structure:
± CH2 CF2 x CF2 CF OCF3 y C2 F4 z ± with x 4; y 1 and z trace
In 1966, NASA [379] published a report describing similar interest, dealing with the copolymerizations
Table 7
Monomer reactivity ratios for copolymerization of VDF (A) with other ¯uoromonomers (B) (and E)
Monomer B rA rB rA r B 1/rA References
H2CyCH2 0.05 8.5 0.42 20.00 [315]

FCHyCH2 0.17 4.2±5.5 0.71±0.94 5.88 [184]
0.20±0.43 3.8±4.9 0.76±2.11 2.33±5 [364]
H2CyCFCF2ORF 0.38 2.41 0.92 2.63 [185]
F2CyCFH 0.70 0.50 0.35 1.43 [365]
F2CyCHCF3 9.0 0.06 0.54 0.11 [187]
F2CyCHC6F13 12.0 0.90 10.80 0.08 [366]
CFClyCF2 0.73 0.75 0.55 1.37 [318]
0.17 0.52 0.09 5.88 [367]
CFBryCF2 0.43 1.46 0.63 2.33 [318]
CF2yCF2 0.23 3.73 0.86 4.35 [318,321]
0.32 0.28 0.09 3.13 [183]
CF3 ±CFyCF2 6.70 0 0 0.15 [196]
2.45 0 0 0.40 [321]
2.90 0.12 0.35 0.34 [195]
F2CyCFOCF3 3.40 0 0 0.29 [192]
F2CyCFOC3F7 1.15 0 0 0.86 [192]
F2CyCFO(HFP)OC2F4SO2F 0.57 0.07 0.04 1.75 [192]
CF2yCF(CH2)3OAc 0.17 3.26 0.59 5.56 [189]
F2CyCF(CH2)3SAc 0.60 0.41 0.25 4.07 [190]
F2CyC(CF3)COF 7.60 0.02 0.15 0.13 [186]
of VDF with F2CyCFOCnF2n11 n 1; 2; 3 initiated by AIBN at high pressure P . 1000 atm: This
synthesis led to ¯uoroelastomers with Tgs ranging from 225 to 2208C.
More recently, PMVE or per¯uoro-n-propyl vinyl ether was shown to readily copolymerize with VDF
in solution, initiated by peroxides, and yielded elastomers with interesting elastomeric behavior since Tgs
were as low as 2448C [192,380].
PAAVE was also copolymerized with VDF and produced original copolymers having low Tgs. For
example, Yamabe et al. [381] from Asahi performed the following emulsion copolymerization:
VDF 1 F2 CyCFOCF2 CF CF3 OC3 F7 ! poly VDF-co-PAAVE
which led to ¯uoroelastomers, the Tgs of which ranged from 236 to 2298C. They showed excellent low-
temperature resistance, alcohol resistance and high thermostability Tdec 390±4158C: In certain cases,
these authors carried out ternary polymerization of these above comonomers with either per¯uoro-n-
propyl vinyl ether or 2-bromo-per¯uoroethyl vinyl ether.
Researchers at the Daikin Company [271] used a comonomer with three ether bridges such as
F2CyCF[OCF2CF(CF3)]2OC3F7 to be copolymerized in a solution process (in 1,2,2-tri¯uorotrichlor-
oethane), initiated by a chloro¯uoroperester. The Tgs of certain copolymers could reach 2448C.
5.7.2. Copolymerization of VDF with functional PAVE or PAAVE

Functional per¯uoroalkoxyalkyl vinyl ethers and mainly those containing a sulfonyl ¯uoride or their
derivatives were also successfully copolymerized with VDF in various processes.
First, Ezzel and Carl [382] encompassed copolymers of VDF and per¯uorovinyl ethoxy sulfonyl
¯uoride.
Then, Connolly and Gresham [383] disclosed the copolymerization of VDF with per¯uorosulfonyl
¯uoride ethoxy propyl vinyl ether (PSEPVE) and the terpolymerization involving HFP, in an emulsion
process, but using a small amount of functional comonomer so that only 0.2±5.0 mol% was present in
the copolymer.
Recently Feiring et al. [384,385] have also investigated on the copolymerization of VDF with various
functional comonomers as F2CyCFOCF2CF(CF3)OC2F4R where R represents NHSO2CF3 (described by
Desmarteau [289] or Xue [386]), SO2CLi(SO2CF3)2, SO2NLiSO2CF3 and SO2F (PSEPVE) [385]. In the
case of the last system, the copolymers have a Tg of 2208C and no weight-loss was noted up to 3758C.
Hence, these copolymers with pendant groups containing ¯uorosulfonyl methide or ¯uorosulfonyl
imide derivatives are original ¯uorinated ionomers that can be used in applications such as batteries, fuel
cells, electrolysis cells, ion exchange membranes, sensors, electrochromic windows, in electrochemical
capacitors and for modi®ed electrodes.
More recently, we have disclosed that VDF copolymerizes with PSEPVE [387] in all proportion and
have been able to assess their reactivity ratios (Table 7). More interestingly, the addition of HFP in this
system enabled the functional PSEPVE monomer to improve its reactivity and to produce original
elastomers with a higher thermostability [388].
5.8. VDF/functional per¯uorovinyl monomers
In contrast to the above-mentioned per¯uorovinyl ethers that propagate with dif®culty in radical
polymerization (only hydroxy-terminated per¯uorovinyl ethers homopolymerize under ionic conditions
[284]), several attempts of copolymerizations of VDF with F2CyCF±R±G (where G and R represent a
functional group and a hydrogenated spacer, respectively) have shown that these latter homopolymerize
easily. Such original monomers enable the resulting copolymers to be ef®ciently crosslinked with routes
different from those usually involved (by means of diamines, bisphenols, peroxydes or by radiations, as
reported in Section 7).
Pioneering work was carried out by researchers at Daikin [389] from various functional monomers
such as: F2CyCF(CF2)n(CH2)mOH where n 0; 1; 2 and m 1±3:
The synthesis of the monomers was described in the same patent, while the optimization of
F2CyCF(CH2)3OR (with R H or Ac) was recently achieved [390]. Other functional tri¯uorovinyl
monomers have also been prepared: either bearing an v-insaturation [391±393], or a carboxylic
[394±396], an amide [392], a sultone [391], an epoxide [397], a hydroxyl [188,394,398], a thioacetoxy
[190] and a phosphonate group [399]. More exotic routes to tri¯uorovinyl end-group have been reviewed
recently [400]. In addition, tri¯uorovinyl monomers bearing nitrogenated heterocycle have been
reported already [401]. Copolymerizations of VDF with F2CyCF(CH2)3OR [189,389] or with
F2CyCF(CH2)3SCOR [190,402] were achieved leading to elastomeric materials (according to the nature
and the amount of the functional monomer, Tgs were ranging from 223 to 288C [389]). Their kinetics of
copolymerization were also investigated, showing that the reactivity ratio of VDF was lower than that
of the functional comonomer [189,190] (Table 7). Indeed, it was worth supplying a reactivity series of
¯uorinated monomers about VDF. The traditional method for the determination of relative reactivity of a
macroradical to several monomers was used. Indeed, it is common to compare the values 1=rA
kAB =kAA as the ratio of rate constants of crossed propagation to that of propagation (kAA). Thus, the
higher the 1=r value, the more able the radical is to react with the second monomer. Table 7 allows one to
suggest the following series of relative reactivities of monomers to VDF• radicals.
F2CyCHC6F13 , F2CyCHCF3 , HFP , PMVE , PPVE , VDF , TrFE , CTFE (recent value) <
BrTFE , H2CyCFCF2ORF , TFE , F2CyCFC3H6SCOCH3 , F2CyCFC3H6OAc , H2CyCHF <
CTFE (old value) , E, although numerous kinetics still deserve to be investigated, as that involving
VDF and F2CyCFCO2CH3, showing in a ®rst attempt that VDF incorporates the copolymer better [320].
6. Fluoroelastomers containing heteroatoms
Besides the common ¯uorinated elastomers described above, containing carbon, ¯uorine, hydrogen,
and in several cases, small quantities of oxygen, other elastomers having heteroatoms have also been
developed. Five main families are summarized below, including ª¯uoroinorganicº elastomers such as
¯uorophosphazenes and ¯uorosilicones.
6.1. Poly(thiocarbonyle ¯uoride)s
The CyS bond is able to be polymerized by means of an anionic initiation [403,404] at low tempera-
tures to lead to ¯uorinated polymers containing low Tgs. Various examples of structures are the follow-
ing [403,405±407]: ±(CF2S)n ±; ±[C(CF3)2S]n ± and ±[CF(RF)S]n ± where RF designates a per¯uoroalkyl
group.
6.2. Fluorinated polyethers and per¯uoropolyethers (PFPEs)
PFPE, which also constitute a special class of ¯uoropolymers, have found various applications such as
lubricants [408], elastomers [409], pump ¯uids and heat transfer ¯uids under demanding conditions.
Four main families of ¯uorinated polyethers are produced in an industrial scale. These are Fomblin w,
Krytox w, Denmum w and A¯unox w produced by Ausimont, Du Pont, Daikin and NOK Corp. (or Nippon
Mektron Ltd), respectively [409].
These polymers are prepared by anionic ring opening polymerization of HFPO (PFPE-K) [409±412],
by polymerization of TFE or HFP in the presence of oxygen under UV(PFPE-Y and PFPE-Z) [408,409]
or by Lewis acid-catalyzed ring opening polymerization of 2,2,3,3-tetra¯uorooxetane followed by a
direct ¯uorination under UV light (PFPE-D) [413]. Lagow et al. [414,415] also achieved their syntheses
by direct ¯uorination of hydrogenated polyethers; this process requiring much care to avoid side-reac-
tions such as cleavages of chains. Nowadays, the production of the PFPE from this last way is developed
by Ex¯uor Research Corp. [416,417].
Their interesting characteristics are their low Tgs (lower than 2508C) and their totally amorphous state
thanks to their aliphatic structure and ether links [409,415]. In addition, these products, endowed with
high thermostability, excellent chemical inertness and low surface tension, ®nd relevant applications as
lubricants and heat carrier-¯uids in hostile conditions.
PFPE can be homopolymers or copolymers and can exhibit linear or branched structures, as follows:
CF3 OCF2 CF2 p OCF2 q OCF3 n , 13; 000
4000 , M Fomblinw Z
CF3 CF2 CF2 O CF2 CF2 CF2 On CF2 CF3 n , 7000
1600 , M Demnumw
CF3 CF2 OCF2 CF CF3 n F n , 10; 300

1300 , M Krytoxw
CF3 OCF2 CF CF3 Op CF2 On CF3 n , 7000

600 , M Fomblinw Y
CF3 OCF2 CF2 p OCF2 CF CF3 q OCF2 r OCF3 n , 10; 000
900 , M Fomblinw K
±O±CF CF3 CF2 n ± n , 16; 600

1350 , M Aflunoxw or Aflunoxw V
In a smaller scale, the Hoescht Company develops HFPO polymers leading to ¯uorinated polyether
acryl ¯uoride which, after hydrolysis and decarboxylation, becomes Hostinert w PFPE [418].
Functionalized PFPEs are well reported by Scheirs [409] while most investigations have been
performed by Ausimont [419]. They are:
HO2 C OC2 F4 p OCF2 CF CF3 q OCF2 r CO2 H Fomblinw Z-diac
HOCH2 OC2 F4 p OCF2 CF CF3 q OCF2 r CH2 OH Fomblinw Z-diol
CH3 OCO OC2 F4 p OCF2 CF CF3 q OCF2 r CO2 CH3 Fomblinw Z-diol
In addition DuPont develops a PFPE with an iodo end-group, leading to original PFPE-b-poly(VDF-
co-HFP) diblock copolymers under telomerization conditions [420]:
rad:
PFPE±I 1 nVDF 1 pHFP ! PFPE-b-poly VDF-co-HFP
According to the nature of the initiator and to the stoichiometry of the reaction, molecular weights
ranging between 1900 and 30,000 were obtained [420] (starting from a PFPE-I having a M n 1300:
More recently, an interesting study regarding the synthesis of poly(e-caprolactone)-b-PFPE-b-poly(e-
caprolactone) was achieved from the ring opening polymerization of e-caprolactone by using hydroxyl-
telechelic PFPEs in the presence of various catalyst/initiators [421].
Interesting reviews [408,409,422±424] or articles [425±429] supply pertinent information on the
syntheses, the properties and applications of these PFPEs.
More exotic ¯uorinated polyethers are those prepared by DuPont from the ionic addition of hydroxy
end-group to tri¯uorovinyl ethers [284]. The monomers have the following formula:
F2 CyCFOCF2 CF CF3 OC2 F4 CH2 OH or F2 CyCFOC3 F6 CH2 OH
The polymerization proceeds quickly at ambient temperature leading to oligomers M w
4000±6000: Useful data is reported in the interesting chapter of Hung et al. [284].
These hydrogeno¯uorinated polyethers were photochemically ¯uorinated leading to original PFPEs
[430].
More exotic process, performed in supercritical CO2 was reported, enabling the produced PFPEs to be
involved in coating applications [431].
6.3. Fluoro nitroso elastomers
Nitroso ¯uoroelastomers are heterochain polymers applied mainly to situations where a non-¯am-
mable elastomer is needed or to ambient temperature conditions where resistance to hydrocarbon or
strong oxidizing reagents is required. The ultimate characteristic of the nitroso polymer is failing to burn
in pure oxygen and has resulted in its extensive use for the NASA in the Apollo spacecraft.
The most important of this series is the copolymer resulting from the spontaneous alternated copoly-
merization of tri¯uoronitrosomethane with TFE [432±434] leading to the intermediate oxazetidine:
CF3 N O
CF2 CF2
to yield the following branched nitroso elastomer:

CF3
N O CF2 CF2
n
This polymer has a Tg of 2518C and has demonstrated excellent resistance to corrosive chemical
environments such as hydrogen-bearing solvents, acids, oxidizing agents, ®re and ozone [435,436].
Other analogs utilizing variously substituted nitroso monomers and different ole®ns were also prepared
[437±442]. In some cases, the obtained ¯uoropolymers reached an average molecular weight of 100,000
[440], as elastomeric gums.
Other poly¯uorinated nitrosoalkanes were developed by 3M [443].
The only effective crosslinking agents were found to be diamines but some degradation took place
during the cure and the ®nal products had relatively low tensile strength. A terpolymer in which pendant
carboxyl groups were incorporated afforded a system susceptible to vulcanization by a large selection of
agents. However, the presence of carboxyl groups resulted in somewhat decreased oxidative stability as
compared to the original copolymer system [444].
The nitroso ¯uoroelastomers are not commercialized yet and the future of these materials would seem
to be limited to that of specialty elastomers although numerous investigations have been performed since
more than 60 polymers have been synthesized already [442,445].
6.4. Poly¯uoroalkoxyphosphazene polymers
The poly¯uoroalkoxyphosphazenes represent a recent commercial addition to the ¯uorinated elasto-

mer family. Early work culminated in studies of polymerization conditions conducive to the production
of linear high-molecular weight M n . 106 dichlorophosphazene polymers ±[NyP(Cl2)]n ± known as
inorganic rubber [446]. They can be prepared by heating the hexachlorocyclotriphosphazene cyclic
trimer under vacuum at 2508C and terminating the reaction at moderate (,70%) conversions before
crosslinking occurs. Surprisingly, polyphosphazenes ±[NyP(X2)]n ± have low glass transition tempera-
tures and many can crystallize (e.g. when X F, Tg 2968C and Tm 260 to 2408C; when X Cl,
Tg 2638C and Tm 2308C: Commercial interest as specialty rubbers stems from the preparation of
poly(¯uoroalkoxyphosphazene) elastomers, reported in 1968 [447]. The linear phosphazene polymers

are substituted with ¯uorocarbon alcohols as shown in the following reaction:
±NyP Cl2 ± 1 R1 CH2 ONa ! ±NyP OCH2 R1 2 n ±;

2
where R1 CF3 ; C3 F7 ; R1 CF3 ; T g 2688C
Commercial introduction was achieved by Firestone from 1975 and one of the most well-known
¯uorophosphazenes has OCH2CF3 and OCH2(CF2)4H groups born by the phosphorous atom Tg
2688C: These elastomers are vulcanizable (by peroxide via incorporation of a CSM) and offer a unique
set at low-temperature properties, similar to those of the ¯uorosilicones, with improved oil and solvent
resistance properties from 265 to 11758C. The polymers can be processed on conventional equipment,
vulcanization being achievable via the use of organic peroxides, sulfur with accelerators or high-energy
radiations [448±450]. Excellent resistance is shown by ¯uorinated polyphosphazenes (PNF w elasto-
mers) to ozone, N2O4, hydrolysis by water, ¯ame and radiation, but strong mineral acids lead to a loss of
their properties. The solvent and hydrocarbon resistances, low-temperature ¯exibility and wide service-
temperature range of PNF w elastomers should lead to their utilization in O-rings, fuel hoses, seals,
gaskets, diaphragms and vibration damping.
6.5. Fluorosilicones
As in the previous family, ¯uorosilicones are regarded as ª¯uoroinorganicº elastomers in which

polymeric chains are composed of ªinorganicº repeating units exhibiting organic ¯uorinated pendant
groups. The most important properties are the retention of tensile properties at high-temperature and the
exceptional low-temperature ¯exibility [451,452]. In addition, the introduction of ¯uorine atoms
improves the solvent resistance, although depolymerization occurs from 2308C. As ¯uorophosphazenes,
these polymers contain a ¯uorine amount ranging from 30 to 40%, hence enabling them to get a good
chemical inertness.
Discovered in 1950, regarded as the most common ¯uorosilicones, and leading the market of such a
class of ¯uoropolymers, Silastic w polymers, commercialized by the Dow Corning Company and
prepared from cyclosiloxane D3 [453] has the following repeating base unit:
CH3
(Si O)
CH2 CH2 CF3
The Tg of this poly(methyl tri¯uoropropyl siloxane) ranges from 275 to 2658C and unlike poly(dimethyl
siloxane)s, it does not exhibit a low-temperature crystallization at 2408C, due to the inability of the
polymeric chain to pack into a crystalline lattice [451]. It can be crosslinkable from various classical
processes of the chemistry of silicones such as in the presence of peroxides or from the SiH/Si±CHyCH2
systems [452].
However, the relatively low strength limits the use of ¯uorosilicones to static applications such as
seals for fuel line [454].
To improve the thermostability of such ¯uoropolymers, researchers at the Dow Corning Company
synthesized ªhybridº ¯uorinated silicones with the following structure [455,456]:

R1 R1
Si (CH 2 )n RF (CH 2 ) Si O
n
R2 R2 p
where R1 , R 2 : CH3 , C 2 H 4 CF 3 and RF : (CF2 )x x = 1 or C2 F 4 OC2 F 4

n=2
Recently, our laboratory has supplied novel hybrid ¯uorosilicones based on ¯uorinated telomers
containing VDF, TFE and HFP base units [104]. The ¯uoropolymers are rather stable in a wide range of
temperatures (Tg , 2 408C and Tdec 4008C) [457±461]. Their structure is similar to that above with n
2 or 3; R1, R2: CH3, C2H4CF3 or C2H4C4F9 and RF: (VDF)a (TFE)b (HFP)c with a 0; 1; b 2; 3; c 0; 1:
7. Crosslinking of ¯uoroelastomers
7.1. Introduction
Fluoroelastomers, like all other thermosetting elastomers, require curing in order to get useful and
enhanced properties. A considerable amount of effort has been devoted over the 40 years of existence of
¯uoroelastomers towards the development of practical crosslinking systems. Fluoroelastomers can be
cured by nucleophiles such as diamines or bisphenols, with peroxides and by radiation.
Irrespective of the curing system the best vulcanizate properties are obtained by a two-step process.
The ®rst step comprises both heat (150±1808C) and pressure (10±30 MPa), by molding a specimen in a
press (e.g. compression molding). The second step (post-cure) is carried out in air at 200±2508C at
atmospheric pressure for 12±24 h. Post-curing is utilized to develop optimum physical properties. The
cure chemistry for a variety of ¯uoroelastomers is rather different but there are two basic mechanisms:
ionic and radical curing. These mechanisms are generally considered while the speci®c features of the curing
of various groups of ¯uororubbers have been detailed by various authors [15,19,22,221,348,462±466].
The largest group of ¯uoroelastomers, VDF-based ¯uorocarbons, can be crosslinked by ionic curing;
however, radical curing can also be possible if the polymer has been prepared in the presence of a CSM
bringing a functional group susceptible of a radical attack, such as bromine or iodine [20,22±24].
The cure chemistry of VDF-based ¯uoroelastomers is connected with the strong polarity of the C±F
bond and speci®c polarization of molecules, which determined their selective ability to split off hydro-
gen ¯uoride under the in¯uence of internal factors (e.g. temperature, bases, etc.).
7.2. Ionic curing
VDF/HFP and VDF/HFP/TFE ¯uorocarbon elastomers can be crosslinked by bisnucleophiles, such as

bisphenols and diamines. Schmiegel, in 1979, identi®ed the triad monomer sequences as ªbase-sensitive
sitesº by 19F NMR spectroscopy [358,467]. He observed that solution reaction of VDF/HFP copolymers
in the presence of base results in the decrease of the integral intensity of the signals at 275.2 and
2108.6 ppm in the 19F NMR spectra, corresponding to HFP/VDF/HFP sequence, or in the case of
copolymer with TFE to the following triad sequences: HFP/VDF/TFE and TFE/VDF/TFE.
Fig. 1. Curing of VDF-containing ¯uoroelastomers with diamines.
According to the currently accepted mechanism the crosslinking reaction consists of two steps:
1. dehydro¯uorination of the polymer by the base, to generate double bonds in the backbone chain:
base
sCH±CFr ! sCyCr
2 HF
2. nucleophilic addition of the Nu±R±Nu bis-nucleophile to the double bond, yielding crosslinks:
Nu R Nu
The accelerator, which has the typical structure of phase transfer catalysts (PTC), is thought to act as
the cation of the base, making it able to diffuse through the rubber.
The formation of double bonds in the presence of a base from these base-sensitive sites is the starting
step in the ionic crosslinking of these ¯uoroelastomers. The following reaction mechanism has been
proposed recently by Arcella et al. [22] on the basis of a broad study involving solution investigations
using 19F and 1H NMR, FT-IR techniques, coupled with solid-state curing experiments [468]. The
mechanism is depicted above where the Nu±R±Nu bis-nucleophile represents a bisphenol or a diamine
crosslinker.
In the ®rst step, the formation of ±C(CF3)yCH± double bond by elimination of ¯uorine from the
tertiary carbon is suggested. Double bond is shifted, catalyzed by ¯uorine ion and the formation of ±
CHyCF± double bond occurs. Then, the nucleophilic addition of a crosslinker to the ±CHyCF± double
bond proceeds with:
1. the allylic shift of ¯uorine providing the new ±C(CF3)yCH± double bond;
2. addition onto the double bond followed by elimination of ¯uorine from the same double bond.
7.2.1. From amino systems

Amines or amine-based compounds are used as curatives for ¯uoroelastomer compounds [469±472]
and they are always used in conjunction with magnesium oxide. Aliphatic amines and polyamines were
the earliest curing agents of FKM w elastomers but they are too much reactive, i.e. they tend to scorch
during cure. This drawback has led to the development of carbamate salts of amines and other Schiff
bases [473] which are less reactive. Because of the processing dif®culties and the relatively poor
retention of physical properties at high temperatures (2008C), the importance of the diamine cure has
decreased.
The mechanism of crosslinking involving 1,6±hexanediamine is shown in Fig. 1.
7.2.2. From bisphenol system

Bisphenol cures were developed in the late 1960s and started replacing the diamine cure in the early
1970s.
Schmiegel [358] found that the bisphenol does not react with the polymer without any accelerator,
which is an onium (phosphonium, ammonium, etc.) salt in combination with a metal compound as an
activator. The bisphenol reacts with the metal oxide to give the phenolate ion which, in turn, reacts with
the phosphonium or tetraalkylammonium ion to give the intermediate I or II, respectively. These
intermediates are strong bases which have some compatibility with the polymers and abstract hydrogen
¯uoride from the polymer backbone:
R4 P12 OArOH R4 N12 OAr±OH
I II
The double bonds rearrange and a second molecule of HF can be abstracted from the polymer to give a
diene too. Such reactions are only possible when the CH2 group on the backbone is ¯anked by CF2 or
CF(CF3) groups rendering the hydrogen atoms acidic enough to be abstracted by the base. The resulting
anion will then eliminate a ¯uorine ion and form a double bond and eventually a diene. Formation of the
unsaturation in the polymer backbone is the rate determining step of the curing reaction [19].
The use of a phase transfer catalyst (onium salt) determines the phenolate-anion generation in the
curing reaction to its use up in the rubber compound. For example, the mechanism is as follows:
R4 P1 X2 1 Ca OH2 ! R4 P12 OH 1 CaXOH 3
R4 P1 OH2 1 HO±Ar±OH ! R4 P12 OAr±OH 1 H2 O 4
R4 P12 OArOH 1 F±Polym ! R4 P1 F2 1 Polym±OArOH 5

The R4P 1F 2 obtained diffuses on the Ca(OH)2 surface, where it enters in reactions (3) and (4), and the
cycle is repeated till full exhaust of the bisphenol as a crosslinking agent. The rate and the product of the
reaction depends on the rate of desorption of the ion-pair R4P 12OArOH from the surface of Ca(OH)2
particles and its diffusion into the rubber phase [474,475].
It is suggested [358,467] that the crosslinking reaction proceeds on the macromolecular chain frag-
ments where the HFP/VDF/HFP triads were formed. Under the action of the anion, the reactions of
dehydro¯uorination, double bond rearrangement and again dehydro¯uorination, take place consecu-
tively. The substitution for ¯uorine atoms at unsaturated carbon atoms with phenolate-ion results in
crosslinking. The quaternary salt catalyst regenerates repeatedly, hence its amount in the compound is
several times lower than that of the stoichiometric one. The reaction of crosslinking continues to the use
up of the bisphenol.
Because of processing and property advantage, the most commonly used compound is ªbisphenol-
AFº (2,2 0 -bis(hydroxyphenyl) hexa¯uoropropane) [475]. Others, like hydroquinone, substituted hydro-
quinones and 4,4 0 -disubstituted bisphenols are used commercially to a lesser extent [476]. The bisphenol
reacts with polymer in the presence of an accelerator (PTC), such as phosphonium or ammonium salt, a
compound having the formula:
+
R2
R1 P R3 X (-)n
R4
n
where P is mainly selected from phosphorous, arsenic, and antimony; Ri are substituents such as alkyl,
aryl, aralkyl, and alkenyl; and X is selected from the following groups: halide, sulfate, sul®te and
carbonate [462]. The accelerator is preferably benzyl triphenyl phosphonium chloride or bromide.
The metal compound, as an activator of ionic curing, is composed of a divalent metal oxide, such as
MgO, ZnO, CaO or PbO, or a divalent metal hydroxide or a mixture of oxide and/or hydroxide with a
metal salt of weak acid [462]. The metal compound serves a dual purpose. It absorbs certain gaseous and
acidic materials which are involved during the curing and can chemically attack and weaken the
¯uoroelastomers. It also provides a long-term aging stability. In the process of curing with diamines,
the acid acceptors have been found to play a multirole, since these compounds can affect dehydroha-
logenation, assist in hydrolysis of the Schiff base and regenerate the free amine from its hydro¯uoride
[464].
Fluoroelastomers containing PAVE are not usually cured with bisphenols [23]. They would loose
tri¯uoromethoxide (especially in the most used PMVE) during the dehydro¯uorination step [477].
Tri¯uoromethanol is further degraded to HF and CO2, which results in the formation of large amount
of volatiles and sharply deteriorate sharply the physical properties of these vulcanizates. Patent literature
describes some degree of success when using bisphenol cures with tetrapolymers, containing the four
major monomers: TFE, VDF, HFP and PMVE [478,479].
The main drawback of bisphenol cures is the presence of some unsaturation in the vulcanized parts.
Dehydro¯uorination which occurs in the ionic crosslinking reaction produces double bonds beyond
that which are strictly required for the crosslinking itself. While Smith and Perkins [480] found that four
moles of F 2 per mole of crosslink during the curing by diamines, Schmiegel [358,467] predicted six
moles of F 2 were necessary per mole of crosslink by bisphenol-AF in the presence of quaternary
Fig. 2. Main reactions of proposed crosslinking mechanism of brominated ¯uoroelastomers from peroxides/trially(iso)cyanu-
rate system.
phosphonium salt. Other authors found even higher amount in bisphenol crosslinking depending on the
relative amount of a phosphonium salt [474]. Excess of unsaturations formed in ionically crosslinked
elastomeric parts represent weak points susceptible to further nucleophilic attack by basic substances
present in the contact ¯uid.
There are different ways to overcome that ªAchilles' heelº. One of the possibilities which has been
achieved already lies in forming different ¯uorocarbon elastomer structures, such as ¯uorocarbons
without VDF [218,219] or ¯uorocarbon elastomers without HFP [e.g. TFE/P (A¯as w), TFE/PAVE
copolymers (per¯uoroelastomers), etc.].
An interesting approach was developed by Arcella et al. [220] of so-called protective monomers. The
basic idea was to introduce a monomer able to alter the base-sensitive monomer triads, and produced
new monomer sequences with a lower weakness to nucleophiles [89]. Alternatively, bisamidoxime
compounds were interestingly acting as vulcanizing agents when the copolymer contains nitrite side
groups [481].
But the main route to avoid the presence of unsaturations after the crosslinking reaction is radical
curing, mainly by peroxides.
7.3. Radical curing
7.3.1. Peroxide curing

Peroxide crosslinking is basically a free radical process. It involves the thermal decomposition of
peroxide to provide free radicals which abstract hydrogen from the methylene groups along the polymer
chain, and the resultant polymeric radicals interact, directly or through the intermediary of radical traps
to form crosslinks.
Two different pathways to increase the ef®ciency of peroxide cure vulcanization of ¯uoroelastomers
have been developed. The ®rst one concerns the increase of the content of hydrogen-containing groups
in the copolymer, such as in TFE/P copolymers (A¯as w). The hydrogen of tertiary carbon atom in
propylene units is a little screened (only from one side from ¯uorocarbon groups the energy of the
C±H bond is lowered by the induction effect of CH3 groups). So, these types of H atom are easily
accepted by free radicals with a high yield of polymeric radicals and formation of crosslinks.
These polymers are cured by a peroxide coagent (i.e. radical trap) system. Among the various
peroxides and coreagents, a,a 0 -bis(t-butyl-peroxy)diisopropyl benzene and triallyl isocyanurate
(TAIC) and triallyl cyanurate (TAC) (Fig. 2) are most suitable, respectively [20±24,365,464].
Peroxides, in the presence of acid acceptors, appear to afford good vulcanizates, both with Viton w and
Kel w-F ¯uoroelastomers. This is mainly true for aromatic peroxides since the results with the aliphatic
compounds do not seem to be very encouraging. Investigations were essentially centered on benzoyl
peroxide formulations, although a limited effort was developed using 2,4-dichlorobenzoyl peroxide
[464].
Attempts were made to determine the extent of peroxide crosslinking in the absence of an acid
acceptor, but the properties were not satisfactory. In analogy with the amine series, the optimum proper-
ties are reached [464] only after post-curing.
To make these elastomers better curable by peroxides, a CSM susceptible to free-radical attack has
been introduced [220,482±485]. Bromine-containing monomers such as bromotri¯uoroethylene
[218,268,319,484±490], 1-bromo-2,2-di¯uoroethylene [489], per¯uoro(2-bromoethyl vinyl ether)
[220,259,260,491±496] and others [268,273,482,483,486,496±499] provide such cure sites (Fig. 2).
Adding tributyl stananne or triethyl silane improves the curing [496]. It is desirable that the bromomo-
nomers copolymerize to high conversion with minimum chain transfer and inhibition. For good curing
performance, an aliphatic peroxide, a suitable radical trap, and an inorganic acid acceptor are required.
Among the various peroxides tried, 2,5-dimethyl-2,5-di-t-butylperoxyhexane (peroxide I) and 2,5-
dimethyl-2,5-di-t-butylperoxyhex-3-yne (peroxide II) were found to be the most suitable. Peroxides
that contain aromatic substituents such as dicumyl peroxide, give variable results, and may be linked
to their sensitivity to acid catalyzed decompositions. The preferred coreagent or radical trap is TAIC.
The other common radical traps are similarly effective in formation of crosslinks, but the resulting
networks are less stable, as determined by compression set resistance measurements at 2308C [269].
The crosslinkers are usually di- or trifunctional electron-rich ole®ns [269], such as TAIC (Diak w 17),
TAC and trimethallyl isocyanurate (Diak w 8) [269]. The radical trap (coagent) concentration is impor-
tant to maintain both a good cure rate and a ®nal cure state.
The introduction of iodine-containing ¯uoroelastomers facilitates the molding process considerably
and makes possible injection molding of ¯uoroelastomers. I/Br-¯uoroelastomers combine the properties
from iodine as chain end [100±104,497,500] and from Br in the polymer chain [107,108,464]. The
reaction mechanism of peroxide curing with coagent is well known and described in the literature
[15,17±24,269].
The radical produced from the initiator may abstract an X-atom from the polymer (minor reaction) or
add to the radical trap (e.g. TAIC) to give a more stable radical (Fig. 2). These more stable radical
intermediates, in turn, abstract X atoms from the polymer, generating polymeric radicals. The driving
force for such a chain reaction during propagation is the transfer of an X atom from the electron-poor
¯uoropolymer to the electron-rich hydrocarbon radical on the radical trap. The radical trap, therefore,
becomes the crosslinker and to give optimum properties should be ef®cient (multifunctional and elec-
tron-rich) and thermally and oxidatively stable.
Metal oxides are useful in absorbing any traces of HF generated during the curing process [269]. As a
result, such polymers show a marked improvement in steam and acid resistance, together with good
physical properties of vulcanizates.
Arcella et al. [220,259] suggested an interesting idea to prepare mixed hydroxilic/peroxidic network
to reduce double bond formation of ionic crosslinking. In this way, it is possible to reduce the amount of
onium salt and compensate the reduced crosslinking density by curing of brominated chain-ends using a
peroxide system. A new peroxide cure system was introduced by Saito et al. [501] for VDF-based
¯uoroelastomers. It is a combination of radical curing system, promoted by a special organic onium
compound and acid acceptor. A radical generated from organic peroxide adds to TAIC to give a TAIC-
radical. Simultaneously, dehydro¯uorination of the elastomer backbone occurs in the presence of onium
compound and acid acceptor, followed by the addition of the TAIC radical across the generated ¯uoro-
ole®n cure site. These steps occur during the curing period.
7.3.2. Other system of radical curing

For example, although thiol-ene systems have easily led to vulcanize hydrogenated elastomers, this
process has been used scarcely to cure ¯uoroelastomers because of the dif®culty in the availability of
mercapto side groups. However, we have recently used an original tri¯uorovinyl v-thioacetate monomer
(FSAc) able to copolymerize with VDF [190], and the resulting copolymer was hydrolyzed to generate
elastomers bearing mercapto lateral groups (copo SH). Curing was performed in the presence of
non-conjugated dienes as follows [190,402]:

UV
F2 CyCFCH2 CHyCH2 1 HSCOCH3 ! F2 CyCFC3 H6 SCOCH3
FSAc
rad:
FSAc 1 F2 CyCH2 ! poly VDF-co-FSAc
poly(VDF co FSAc) KCN (C2 F2 H2 ) (CF2 CF )

n p
C3 H 6 SH
copo SH
PVDF
(CH 2 )3 (CH2 )3
S S
copo SH + H2 C=CHC 2 H4 CH=CH 2 rad. (CH2 )6 (CH2 )6
S S
(CH2 )3 (CH2 )3
PVDF
Other systems of crosslinking more adapted to TFE-containing elastomers are detailed in Section 7.6.
7.4. Radiation crosslinking of ¯uoroelastomers
Fluorinated polymers containing hydrogen (including VDF-base copolymers) and copolymers of TFE
and HFP can be crosslinked with different degrees of effectiveness by high-energy radiation. In the last
15 years several outstanding reviews of radiation crosslinking of ¯uoropolymers have been published by
Lyons [502±504] and many articles detail different aspects of this process, more recently reported by
Logothetis [505] and Forsythe [506,507]. Indeed, Dixon et al. [348] were the ®rst team to disclose that
VDF/HFP elastomers could be cured successfully with high-energy radiation. Then, Florin and Wall
[508] performed further studies of VDF-based copolymers and Yoshida et al. [509] studied the stress
relaxation of irradiated ¯uorocarbon elastomers.
The mechanism of radiation crosslinking of ¯uoroelastomers is similar to that proposed for other
elastomers: it is a typical radical mechanism closed to peroxide curing. In irradiated products, the free
radicals were registered. But even at such high-energy irradiation the free ¯uorine was not found.
Hydrogen ¯uoride is produced during the irradiation of VDF copolymers but having a great bond
strength, it does not participate in exchange reactions along the polymer chains. Hence, in hydrogen
containing ¯uoropolymers, it may be assumed that only exchange reactions of hydrogen atoms or main
chain radicals can be expected [510]. Depending on the copolymer compositions, different doses are
required for radiation curing: for VDF/CTFE copolymers, low doses up to 3 Mrad are enough, while for
VDF/HFP elastomers, 10 Mrad and more [510] were necessary.
Post-curing is also needed to improve the technical properties of vulcanizates. The presence of radical
traps (TAIC and others) increases the ef®ciency of radiation curing. Mainly carbon±carbon crosslinks
Fig. 3. Thermal curing of nitrile-containing ¯uoroelastomers.
are formed, and it may be expected to have a good resistance to heat aging, and a relative inertness to
chemical and oxidative attack. This process was applied successfully for TFE/P copolymers [248].
Radiation vulcanization can be accelerated in the presence of the sensitizers, such as vinyl ethynyl-
phenylol resins or other unsaturated compounds [511]. In this way, the total dose for optimum cross-
linking can be lowered and the properties of gum can be considerably improved.
Doses of 10±15 Mrad are suf®cient to give excellent properties and the cured parts remain clear and
colorless [504]. There seems to be little selectivity, i.e. crosslinked parts with good properties have been
made from polymers containing functionalities and from those without any functionality. The advantage
of radiation cured materials is that they do not contain any ®ller or chemical, i.e. any impurity that can be
extracted from the vulcanizates which is so important in the semiconductor industry [24].
7.5. Post-curing of ¯uoroelastomers
Post-curing of ¯uoroelastomers is more applied for chemical curing than for radiation crosslinking
and leads to improvement of the mechanical properties of the ®nal vulcanizate. Indeed, an increase (ca.
50%) is noted in the Young's modulus and the tensile strength at break, while a 50% decrease is seen in
elongation at break and a substantial improvement in compression set resistance [477]. One of the
essential functions of the oven cure is the removal of water, a by-product of the cure, the presence of
which prevents full development of the diamine cure and causes reversion of the bisphenol cure
[471,480]. Smith and Perkins [480] showed that post-cure would enhance another type of crosslinking.
They suggested the formation of aromatic rings with loss of HF by a Diels±Alder addition. However, in
other works [269,512±519] it was concluded that during post-cure a thermally induced bond-breaking
and bond-making process occurs and this results in a more stable network. However, the present
mechanism of post-curing reaction is not completely understood.
7.6. Curing chemistry of TFE-based per¯uoroelastomers
Per¯uoroelastomers (FFKM w, Du Pont products [4,19]: Kalrez w, Perlast w are based on copolymers of
TFE (60±80 mol%) with PAVE (20±40 mol%) and a third CSM in less than 2 mol%. The most readily
copolymerizable homolog is PMVE. The CSM comprises the following three classes of compounds [24]:
1. per¯uoro(alkylvinyl ethers), CF2yCF±O±RF ±G; where G designates ±COOR, ±OC6H5,

±O(CF2)nCN, ±CN, ±Br;
2. substituted ¯uoroole®ns such as R1CHyCR2R3; R1, R2, R3: H, Br, F, RF, RFBr;
3. ¯uoroiodo compounds, RFI and IRFI; RF: per¯uoroalkyl group.
For the curing process of FFKM w of great importance are per¯uoroole®ns containing Br and I atoms
[520±522] or PAVE, containing nitrile groups. Vulcanization of per¯uoroelastomers with nitrile groups
is brought about by the catalytic interaction of tetraphenyltin or silver oxide on the pendant CN group,
thereby creating a triazine crosslinked structure [19±24].
Typically, the ±CN end-groups of the grafts enable the ¯uoroelastomer to be cured leading to stable
triazine rings as shown in Fig. 3. These cyano per¯uorinated elastomers display outstanding thermal and
oxidative [303] stabilities and continuing efforts have been directed to further modi®cation of these
polymers to broaden the areas in which they can be used (Section 10).
Per¯uoroelastomers containing bromine or iodine cure site can be crosslinked with aromatic or
aliphatic peroxides in the presence of radical traps, such as TAIC well detailed by Logothetis
[19,20,24,273]. These types of vulcanizate have more universal chemical resistance while thermal
stability is less important.
The iodine-based cure system used with Perlast w is unique and does not afford the level of extreme
high-temperature resistance associated with the triazine-cured Kalrez w 4079. Thanks to this curing,
Kalrez w 4079 is the only elastomer capable of extended service at 3168C. Perlast w system has the
great advantage of containing neither metal oxide nor other metal-based catalysts [222,518].
Aromatic or aliphatic diamines and bisphenols (dipotassium salts) can be used to cure per¯uoroelas-
tomers containing per¯uorophenoxy or hydrogen cure sites. This system, in order to act well, requires
the presence of an accelerator such as polyethers or the cyclic polyether compounds.
Per¯uoroelastomers may also be cured by high-energy radiation.
Clear cured parts can be made by curing per¯uoroelastomers with a high-energy electron beam
followed by a post-cure. The chemical resistance and compression set properties of these materials
are excellent, but the tensile properties are lower because they do not contain any reinforcing ®llers [24].
8. Formulations and ingredients of ¯uoroelastomer compounds
8.1. Introduction
Compounding of ¯uoroelastomers is relatively more simple when compared to other rubbers.

Ingredients are obviously the result of the particular cure chemistry, ®nal properties to be achieved
and processing technology to be used. A summary of ¯uoroelastomer technology is available in the
literature [523±527].
End-use requirements usually dictate the type of ¯uoroelastomers to be used: vulcanization system,
®llers and other process aids. The ingredients do not exert negative in¯uence on chemical and thermal
resistance of ¯uoroelastomers and the curing system has to give a network bonds with similar energy to
the main polymer chain. There are no special stabilizers against heat or aging of ¯uoroelastomers but
inorganic oxides and alkali-earth hydroxides can improve their thermal stability. The ®llers used are not
of any special type: they cannot considerably regulate the mechanical properties and the level of ®lling is
not high. Different processing aids such as low-molecular weight polyethylenes or hydrocarbon waxes
and pigments can also be used. Plasticizers are generally avoided since they in¯uence negatively during
post-cure processing aids. Usually, the standard chemicals are cure systems (curative and accelerators),
acid scavengers (metal oxides), activators (hydroxides), ®ller(s), processing aids and pigments (if
necessary for coloration).
A typical recipe of ¯uoroelastomers can be given as follows (in parts per hundred, phr): ¯uoroelas-
tomer 100; curing system ca. 1±6; metal oxides ca. 3±15; ®llers ca. 0±40; processing aids ca. 0±5;
others (if needed) ca. 1±5.
The simplicity of the ¯uoroelastomer formulations requires an adequate choice of the ingredients of
every group to satisfy the requirements of technological properties of rubber mixtures and operating
properties of end vulcanizates.
This is why some aspects of the choice of different ingredients and their in¯uence to the properties of
rubber mixtures and end-articles are discussed.
8.2. Vulcanization systems
Since the mechanism and chemistry of curing are detailed in Section 7, only the technological aspects
of the curing are reported below.
Three types of cure system used are from diamines, dihydroxy and peroxides. Radiation crosslinking
has also been discussed in a preceding section. The most popular cured system (about 80% of all
applications) is the nucleophilic one. It is based on the crosslinker (mainly bisphenol-AF [474,475])
and accelerator (a phase transfer catalyst).
8.2.1. Block polyfunctional amines

Diamine curing system is the ®rst one applied for the ¯uoroelastomer vulcanization, and the most well
known are DIAK w (trademark of DuPont Dow Elastomers) no. 1 (hexamethylene diamine carbamate),
DIAK w no. 3 (dicinnamylidene diamine carbamate) and DIAK w no. 4 (4,4 0 -bis(aminocyclohexyl)-
methane carbamate). The diamine cure system is characterized by good cures and good bondability,
heat aging and compression set [21]. But they are scorchy (especially nos. 1 and 4), not stable during the
storage, are all sensitive to heat history prior to ®nal processing and prone to mold fouling [523]. Cured
elastomers have relatively low stability to steam and hot water.
8.2.2. Bisphenolic systems

Bisphenolic systems were introduced around 1970 and they dominate the market today. Using these
systems, ¯uoroelastomers can be cured rapidly with good scorchy stability, good compression set values
and improved heat aging properties. They consist of two compounds: curative (usually bisphenol) and
accelerators (quaternary phosphonium or ammonium salts). The most used is bisphenol-AF [2,2-bis(4-
hydroxyphenyl)hexa¯uoropropylidene] in a combination with triphenylbenzyl phosphonium chloride
(BTPPC) [474]. As curatives, others reactants can also be used such as hydroquinone, resorcin with
cation active surfactants (triethylbenzyl ammonium chloride, TEBAC) and others. Curatives and accel-
erators are available as dispersions in low-molecular weight ¯uorohydrocarbon elastomers (ASTMD-
1418 designation FKM w, but suppliers' precompounds dominate.
The recent precompounds have a low viscosity and contain cure systems, which are highly active
above 2008C. They are designed for injection molding at high temperature where the thermally
depressed viscosity allows excellent ¯ow [523]. Bisphenolic vulcanization ensures good technological
properties of rubber mixtures and production of articles with complicate con®gurations. At the same
time they have a high scorchy stability, long-term storage, high rate of curing and excellent compression
set/stress relaxation resistance.
The levels of the acid acceptor (MgO) and activator [Ca(OH)2] in the case of bisphenol cure strongly
affect not only the cure network as re¯ected by the ®nal properties, but also the cure properties so that the
cure system must be ®nely tuned to achieve the optimum balance of processing parameters [22].
8.2.3. Peroxide vulcanization

The peroxide cure system is the most recent of those available and is often combined with co-reagent
(radical trap). In other variants, it requires ¯uoroelastomers where the CSM can be activated. Although
peroxide-curable materials have provided new compound performance, they have not surpassed the
bisphenol cure in many areas. The peroxide cure system consists of organic peroxides and co-reagent
and has had industrial applications from 1976 when ¯uoroelastomers-containing monomers with a
corresponding cure-active site group were developed. The safe processing peroxides most commonly
used are mainly (50%) active 2,5-dimethyl-2,5-di(t-butyl peroxy) hexane or less active 2,5-dimethyl-
2,5-di(t-butyl-peroxy) hexyne-3, typically Varox w DBPH or Luperco w 130 XL, respectively [523]
(Fig. 2). The last one is considered to be more suitable for continuous vulcanization in air or in the
presence of liquid curing medium. The other organic peroxides such as di-(t-butyl peroxide), dicumyl
peroxide and 1,4-di(t-butyl peroxiisopropyl) benzene are also used. Co-reagents such as TAIC (DIAK w
no. 7) or trimethallyl isocyanurate (DIAK w no. 8) enhance crosslink density and hence vulcanizate
properties [523]. Peroxide vulcanizates are characterized with improved resistance to aggressive
aqueous media, to certain lubricant additives and to nucleophilic reagents [527,528], but they give
less scorch safety than the bisphenolic system does. They are required for elastomers, containing
CSM such as Viton w GLT and GFLT, and TFE-P elastomers (A¯as w). In the last case, a combination
of 1,4-di-(t-butylperoxyisopropyl)benzene and TAIC are recommended [529]. Peroxide curing is
preferred in co-vulcanization of ¯uoroelastomers with other synthetic rubbers (e.g. E/P, silicone and
¯uorosilicone rubbers).
Terpolymers, containing in the chain monomer units with nitrile functional end-groups
(CF2yCFO(CF2)4CN and F2CyCFOCF2CF(CF3)OC2F4CN) are cured with tetraphenyltin, Sn(C6H5)4
(3±6 phr) which is a catalyst of trimerization of CN groups, forming thermostable triazine rings
[15,19] (Fig. 3).
Terpolymers, containing per¯uoro-(2-phenyloxypropylvinyl ether), CF2yCFOCF2CF(CF3)OC6H5
can be cured with polyfunctional amines (e.g. hexamethylene diamine) in 1±1.5 phr, introduced with
MgO (10±15 phr) [15,19].
8.3. Metal oxides
Auxiliary active chemicals such as acid scavengers (MgO, PbO, CaO or different inorganic bases) act
at the same time as cure activators to give a high degree of crosslinking [469]. When amine cure system
is used, 15 phr of a low-activity magnesia (iodine no. 20) is typical. For bisphenol cure systems, 3±6 phr
of a high-activity grade (iodine no. 120 1 ) are preferred. Calcium oxide may be added to aid post-cure
of thick components [523]. Where the resistance to aqueous media is needed, the best additive is lead
oxide (fumed litharge), but the health hazards are suf®cient reason to try to eliminate such products from
the inventory. Viton w GBL 205 LF of DuPont (terpolymer of VDF, HFP and TFE containing 68 mol%
of ¯uorine) was shown to have excellent resistance to acid without any need to use lead in the formula-
tion [463].
Metal oxides also improve the ef®ciency of radiation curing of ¯uoroelastomers, but decrease to some
extent the resistance to heat aging in strength state [530].
8.4. Fillers
Filler types and contents are directly dependent on the desired ®nal properties while combinations of
®llers are sometimes the key to the optimization of processing behavior. Generally, the ®llers used in
¯uororubber compounds are rather different from those of conventional elastomers. The reinforced
effect of active ®llers in ¯uoroelastomers is very small and hence non-active or low active carbon
black or mineral ®llers in a typical level up to 50 phr are used [469]. Increasing of the ®ller content
deteriorates the low-temperature properties and heat ageing of ¯uorovulcanizates [15].
MT-black (N-990) is usually the preferred one because of its large particle size and hence increases
the modulus of the crosslinked ¯uoroelastomers.
The incorporation of ®llers results in a higher compound viscosity, lower elongation at break, higher
hardness, modulus and tensile strength [23]. The introduction of low active technical carbon as graphite
decreases the shrinkage of rubber mixture during vulcanization and improved antifriction and wear
resistance of end-products.
Adequate mineral ®llers used in ¯uoroelastomer formulations are barium sulfate, Nyad w 400 (®brous
calcium silicate), Austin black, SRF black (N-774), titanium dioxide, red iron oxide, diatomaceous,
silica and Te¯on w powders. Incorporation of ®ber ®llers such as glass ®bers (diameter of 0.5±3.8 mm,
length of 3±50 mm, coated with organosilanes) and organic ®bers such as phenylon, arimides MP, turlon
in the amount of 5±50 phr improves the heat aging and low-temperature properties of ¯uorovulcanizates
[530,531].
8.5. Processing aids
Fluoroelastomers differ from other synthetic rubbers by their high viscosity and stiffness which make
their processing dif®cult. Hence, process aids are commonly used to assist ¯ow and to improve release
from molds and calenders, to provide a smooth ®nishing for extrudates. They are mainly composed of
two types of ingredient: plasticizers and waxes.
The ®rst one reduces viscosity to improve ¯ow and provides lower hardness parts. The use of
plasticizers in the ¯uoroelastomer formulations is not always expedient, as they deteriorate the mechan-
ical properties, heat and chemical resistances of vulcanizates [532]. Moreover, the plasticizers are
partially evaporated during the post-cure process and this results in poor resistance to compression
set and creep, formation of cracks and pores, especially in thick items [469].
On the other hand, proven process aids include low-molecular polyethylenes, hard waxes such as
Carnauba (a natural wax from bean) or VPA No. 2 and sulfones such as VPA No. 3. Hard waxes in
quantities of up to 1 phr especially assist in demolding, often with 0.5±1.0 phr of an organic sulfone
[523].
A three-component system, speci®cally for peroxide-cured recipes contains 0.25 phr of stearic acid,
0.2±0.5 phr of fatty acid amide and 1±1.5 phr of hard wax [524,525]. In the literature of ¯uoroelastomer
processing, study is shown that useful processing aids can be low-molecular weight ¯uoropolymers or
¯uorocarbon ¯uids, which have a good compatibility with the basic ¯uoroelastomer [526]. Viton w LM
low-molecular weight copolymer of VDF and HFP (about 15 phr [469]), low-molecular weight copo-
lymer of TFE and PMVE with a molecular weight lower than 3 £ 10 4 (1±50 phr [533]) or thermoplastic
elastomers (40±95% soft and 60±5% hard segments [534] can be used to improve the technological
properties of ¯uororubbers, their molding, processability, tensile properties, etc.). Fluorine-containing
poly(meth)acrylates [526,535] CH2yC(CH3)C(O)OCH2CF2CHF2 and Dynamar PPA-790 [536] can also
be used as a processing aids. Polymerizable oligoester acrylates (OEA) with a good compatibility to
¯uoroelastomers were suggested as suitable processing aids. In most cases [537,538], the viscosity of
¯uoroelastomers is reduced, the shrinkage of the vulcanizates is decreased to 2.5% at 20 phr OEA. In the
stage of vulcanization, a graft polymerization of OEA takes place and network particles are formed.
They are bonded with elastomeric macromolecules, acting as vulcanization knots to improve the thermal
and mechanical properties of vulcanizates obtained. The OEA can be used effectively in the radiation
curing of the level of 5±10 phr [539]. To overcome the poor low-temperature properties of ¯uoroelas-
tomers, a blending with other elastomers (polar ones such as acrylic, epichlorohydrine, ¯uorosilicone
and non-polar ones, mainly E/P and silicone rubbers) has been performed [540±542].
Development of peroxide cure systems considerably expands the co-vulcanization of ¯uoroelastomers
with other elastomers, especially ¯uorosilicones and epichlorohydrines. Such products possess a high
heat resistance (up to 2008C) [543], and are resistant to aggressive liquid media (oils, fuels, solvents)
together with good low-temperature properties [527,543].
9. Processing of ¯uoroelastomers
9.1. Introduction
High polarity and molecular weights of the ¯uoroelastomers are their characteristic features over the other
synthetic elastomers and result in a higher viscosity. Besides, the viscosity of rubber mixtures increases after
mixing with a carbon black or with other ®llers. The rheological properties of the elastomer are of paramount
importance because they determine the ¯ow characteristics during mixing, preforming and molding. The
pecularities of ¯uoroelastomers in many cases require a special processing regime, to optimize the cross-
linking density (lower elongation at break, low creep and stress relaxation) with a good tear strength at the
demolding temperature (i.e. less crosslinking or lower-molecular weight [24,523]).
The manufacture of ¯uoroelastomeric items uses typical rubber technology equipment (i.e. that
required for mixing, shaping and curing).
9.2. Mixing
The basic principles in the preparation of ¯uoroelastomer compounds are freedom from any source of
contamination, minimum exposure to water and energy input. Contamination of conventional elastomers
in the course of mixing can deteriorate the serviceability of products made from the mixture. Contam-
ination with unintended compounding ingredients or oils can in¯uence the processing and vulcanization.
Absorption of water from different sources (mainly condensation) accelerates the curing and gives less
scorchy safety. Mixing procedures need to maximize energy input before the matrix becomes too soft
[523].
9.2.1. Open mills

Open milling is quite popular for the processing of ¯uoroelastomers since it needs a lower capital
investment, an easier cleaning of the machine and visual control by skilled operators. But, on the other
hand, the open mills have limited productivity, environmental contamination and poor control [22].
Depending on the ®ller systems, polymer blends and the size of the mills, actual milling time
should require ca. 25±40 min at maximum 80±908C and a roll friction ratio of ca. 1.1±1.25 to 1.0.
The procedure is rather simple. After formation of the rolling bank (temperature 508C for 0.5±3 min)
the metal oxides are added, followed by the ®ller(s), the plasticizers and ®nally the vulcanization
system.
In some cases, to have a better distribution of the cure agent(s) in the mixture, they are introduced with
a small amount of ®ller(s). Crossblends and cigars are rolled several times (e.g. six times). The mixture
prepared is drawn to form a sheet with required thickness and is then cooled. The temperature of the
sheet must be below 80±908C. A formal rework of up to 5 min on cold mills after being allowed to stand
16±24 h is very important to disperse all ingredients completely [523].
9.2.2. Internal mixers

Fluoroelastomers have a high heat build up because of viscous shear and low elongation at break
(called ªgreen strengthº) [544]. When internal mixers are used, intensive cooling and low starting
temperature are necessary to avoid prescorched compounds. A one-pass technique compounding of
¯uoroelastomers can be completed in a 3±5 min cycle. It comprises a charge of ¯uoroelastomer,
introduction of precompounds of metal oxide and carbon black (0.5 min), mixing (1.5 min), addition
of the cure system in the last minute and unloading (for 2±2.5 min at 110±1258C) [469]. Because of
scorch, the amine curing system may be added on the open mills (at a temperature below 708C) or in a
separate internal mixer pass [469]. For the other vulcanization systems, one-pass mixing is used. A high
shear mixing is required to obtain good dispersion, upon which processing and properties depend on a
great extent. Reworking to complete dispersion by mills or internal mixers is recommended. When a
cooling bath is used, it is necessary to remove the stock as soon as possible and to dry with force-air.
The granular beads of ¯uoroelastomers (e.g. Viton w A, A-35, A-HV, B, B-50, E-45, E-60, E-430, GH,
etc) give the possibility of continuous mixing [545].
Fluoroelastomer compounds should only be sampled for rheometer (moving die rheometer, MDR)
and other tests after the reworking step. Fluoroelastomers, their compounds and vulcanizates are tested
according to ASTM or DIN procedures commonly used in the rubber industry.
9.3. Molding
Standard transforming technologies are all applicable for ¯uoroelastomers, such as compression,
transfer and injection molding, extrusion and calendering.
Mass production for large consumption such as O-rings, seals and gaskets is steadily and rapidly
moving towards injection molding [22]. Extruded tubes, hoses and pro®les represent a small percentage
(less than 10%) of the total ¯uoroelastomer consumption.
Molding is the most used process for ¯uoroelastomer compounds. Different factors, such as volume,
tool and equipment amortization ratio of saleable products to scrap, have to be considered to choose the
molding process. Molds should be made from a high-quality Cr/Ni tool steel supplied with a good
temperature control. Mold design should take into account that ¯uoroelastomers may shrink at a differ-
ent ratio, from 2.5 up to 3.0%.
9.3.1. Compression molding

About 60% of ¯uoroelastomers are transformed by compression molding. This process allows ¯ex-
ible, economic production of relatively small volumes of components. The investments in presses and
molds are relatively modest.
The preparation of preforms requires extreme care. They must correspond to the shape and mass of the
components [546]. To minimize scrap, a preform is generally cut or extruded. On the inside parts of the
mold, silicon ¯uid or polyethylene glycol emulsions are usually dispersed. In classic procedures, molds
are set at 170±2008C and the vulcanization time lasts from 30 s to 2 min.
Thanks to the rheological properties of ¯uoroelastomers, the compounds with apparent high Mooney
viscosities (ML/1008C) can be transfer molded. This technique gives a better dimensional control of the
®nished part than those prepared by compression molding [523].
9.3.2. Injection molding

Recent development of ¯uoroelastomers (e.g. polymerization, facilitate cure systems, special ¯uori-
nated processing aids) contributes to their injection mold, applied for high-volume precision parts such
as O-rings and shaft seals [18±24,496]. Fluororubbers compounds with a low viscosity (Viton w A-35 or
B-50) can be processed easily than those of high viscosity. To improve the injection molding, a low-
molecular weight polyethylene and waxes in the level of 0.5±2 phr is preferable [469]. Generally,
injection molding is carried out at relatively low temperatures from 70 to 808C.
Recently, the raw types of bisphenol-cured precompound have been available and the vulcanization
time is only 30 s or less at the mold temperature of 2008C with an outstanding easy release. In the other
cases, external mold release agents are necessary (e.g. with amine cure system, dispersions based on
polyethylene (up to 1808C) or modi®ed silicones are effective) [523].
The best results obtained from injection molding are achieved by vacuum, applied during the injection
step in order to avoid air trapping, splitting and porosity. The mold must be designed to avoid as much as
possible losses in ¯ash, sprue and runners [24].
9.4. Calendering
Calendering is mostly used to produce sheets with or without fabric inserts. Compounds for calender-
ing should be of medium or low viscosity and high elongation grades are preferred for such applications
[523]. The ¯uororubber compounds are calendered at relatively cool rolls; e.g. the temperature of the top
roll is 50±708C, that of the central one is 45±658C while the lowest one is not heated. If there is no
danger of scorch, the temperatures of the top and central rolls can be higher. To avoid any presence of air
in the ¯uororubber compounds and any presence of pores in the sheets, it is necessary to have a high
friction between the top and central rolls, the addition of 3±5 phr of low-molecular weight polyethylene,
and the use of higher molecular weight ¯uoroelastomers (e.g. Viton w A-HV or Viton w B) to improve the
ªgreen strengthº.
9.5. Extrusion
Fluoroelastomers can also be shaped by extrusion [547]. The fully mixed stock is continuously forced
through a shaping die below the curing temperature. The typical temperature pattern for ¯uoroelasto-
mers is a gradual increase from the feeding zone to the die: from cold feed (40±658C), then heating (75±
858C) to die (for a maximum temperature of about 1008C). A roller feed is required. To minimize the
frictional adhesion of hot compounds to the die and to prevent surface fractures the elastomer composi-
tion (processing aids and polymer green strength) and the extruder/die characteristics have to be care-
fully regulated [524,547]. As no practical continuous vulcanization method is used, the cure of extruded
tubes, hoses and pro®les is achieved by steam or air autoclaving.
9.6. Vulcanization
Generally, the vulcanization of ¯uoroelastomers is composed of two stages. The ®rst one consists of
either shaping under pressure in the presses and heating, or vulcanization in autoclave or continuous
curing of sheets and radiation curing. The second step, called post-curing, is provided in a thermostated
oven, usually in air, to develop optimum properties of vulcanizates.
Vulcanization in presses is performed from 170 to 2008C with a vulcanization time ranging from 5 to
60 min and a pressure from 10 to 30 MPa, depending on the type of curing system, con®guration and size
of the parts. Thin parts require up to 4 min at 2008C, but thick ones need 30±60 min at 150±1708C.
Autoclave vulcanization in steam or pressurized hot air is applied for the length parts (tubes, sleeves)
for which the post-cure stage is usually not necessary. The vulcanization temperature ranges from 120 to
1558C with the time from 20 min to 4 hr. Vulcanization that occurs in hot air is mainly applied for
compounds involving peroxide cure systems.
The vulcanization of TFE-P (A¯as w) elastomers can be performed at higher temperatures (1658C for
30 min to 1958C for 3 min). The optimum is reached at 1708C for 15 min while post-curing at 2008C for
3 h [529].
The vulcanization of per¯uorocarbon Kalrez w-type elastomers depends on the CSM and on the cure
system. For example, in the case of ¯uorinated terpolymers containing a CSM that bears nitrile groups
and requiring a vulcanization agent such as tetraphenyltin, the conditions of press vulcanization are
160±2108C, 0.5±18 h and pressure of 7 MPa, followed by a post-curing at 200±2908C for 24±36 h.
The iodine-based cure system used for Perlast w is unique and, whilst not affording the levels of
extreme high-temperature resistance associated with the triazine-cured Kalrez w 4079, the Perlast w
system has the major advantage to contain neither metal oxide nor other metal-based catalysts. The
bisphenol-AF system allows the vulcanizates to withstand temperatures of above 2708C and the more
recent triazine-based system affords vulcanizates which can bear prolonged use around 3168C depending
on other conditions [222].
In the second post-cure stage, an increasing of degree of crosslinking is observed. It is suggested that
crossbonds are formed by the Diels±Alder reactions between adjacent dehydro¯uorinated units, separa-
tion of side-volatile products such as HCl or HF, H2O. Post-curing considerably improves mechanical
Table 8
Chemical resistance of different types of ¯uoroelastomer [221,222,526]: A Ð excellent; B Ð good; C Ð unsuitable for use
Fluid type Fluoroelastomer
FFKM w FKM w TFE/P Fluorosilicone
Solvents
Acetone A C B C
Benzene A A B C
Ethyl acetate A C ± C
Formaldehyde A C ± C
Hexane A A B A
Methanol A B A B
Methylene chloride A B ± B
Methyl isobutyl ketone A B C C
Methyl tert-butyl ether A B C C
Pyridine A C C C
Water A A A A
Acid±base
Acetic acid A B A C
Sulfuric acid A A A B
Aniline A B A C
Sodium hydroxide A B A B
Oil and others
Oxidizers A B B C
Oils and greases A A A A
Halogenated refrigerents B C C C
properties of end-products: the longer the post-curing time, the greater the tensile strength and the lower
the compression set.
Temperatures are typically 2008C (for amine cures and bonded parts), from 230 to 2608C (bisphenol
and peroxide cures) for 16±24 h [523]. Thick parts may also require inclusion of 1±3 phr of CaO to
prevent ®ssuring. Ovens must be positively vented to atmosphere (10 air changes per hour) and not
overloaded (the ¯uoroelastomers cannot exceed 10% of the volume of the oven).
A serious problem for ¯uoroelastomers deals with their high shrinkage and the anisotropy of the
shrinkage from the mold being higher than that of hydrocarbon rubbers. Actually, the anisotropy is
increasing during the post-curing. The reason lies in the different thermal coef®cients of expansion of
mold and rubber mixture. Fillers, notably graphite, decrease the shrinkage, but other ®llers do not
decrease it as in the case of conventional elastomers. During post-curing as a result of extra crosslinking,
loss of process aids, curatives, moisture and other volatile products is observed and the shrinkage grows.
In the press forming, the shrinkage is about 2% and, additionally, in the post-cure oven, it is 1%. For the
¯uoroelastomers, a shrinkage anisotropy is typical. The shrinkage in thickness is higher than that in
length. With the increase of temperatures of the press and of the post-curing process, and by the
introduction of ®llers (e.g. graphite), the shrinkage anisotropy decreases [548]. The shrinkage should
be considered when part tolerances are speci®ed.
Table 9
Temperature of service, massic amounts of ¯uorine and hydrogen in elastomers
Type a Temperature of F (%) H (%)

service, (8C) b
Fluorocarbon elastomers
VDF/HFP 218±210 66 1.9
VDF/HFP/TFE 212±230 66.5±69.5 1.1±1.9
VDF/PMVE/TFE 227±230 64±66.5 1.1±1.7
TFE/propene 0±200 54±57 4.3
TFE/PMVE 0±280 73 0
TFE/PMVE/E 215±230 66 1.1
Fluorosilicone 265±175 37 4.5
Fluorophosphazenes 265±175 55 1.4
a
VDF, vinylidene ¯uoride; HFP, hexa¯uoropropylene; TFE, tetra¯uoroethylene; PMVE, pe¯uoromethyl vinyl ether.
b
Range of temperature in continuous service.
9.7. Safety and environmental considerations
Fortunately, ¯uoroelastomers are non-toxic and non-irritating under normal conditions. They can be
compounded and cured with standard precautions, such as temperature control, adequate ventilation and
so on. Safety information of polymer and ingredient suppliers should always be studied prior to process
¯uoroelastomers for the ®rst time or before introducing a new grade.
10. Properties of ¯uoroelastomers
10.1. Introduction
Fluoroelastomers account for 4% only of the consumption of specialty rubbers but they give excellent
performance under severe conditions requiring great resistance to high temperature and chemical envir-
onments and have a great place in the progress of modern industries. Generally, their properties are
determined versus the ¯uorine content, the structure of the copolymer chain, the ¯uoroelastomer
compounds and their network.
The most commonly used ¯uoroelastomers are usually referred to as A and B types. A types are di-
polymers of VDF and HFP and have a nominal ¯uorine content of 66% by weight. B types are
terpolymers containing VDF, HFP and TFE in a ratio which gives a nominal ¯uorine content of
68 wt%. The decreased hydrogen content of the B-type polymers results in improved chemical
resistance. B-type polymers also have superior high-temperature stability. Adjusting the ratio of
VDF, HFP and TFE to give 70% by weight of ¯uorine results in polymers which are generally referred
to as F types. F-type polymers possess a ¯uid resistance which is superior to those of both A and B types
401 [549].
There are many other specialty grades of ¯uoroelastomers available, which use additional or different
monomers to impact speci®c qualities. Fluorel w ¯uoroelastomers from 3M/Dyneon and Viton w
¯uoroelastomers from DuPont have the ASTM designation FKM w while per¯uoroelastomers are desig-
nated FFKM w.
The following sections exhibit several examples of properties such as the chemical inertness, the
thermal stability and the mechanical properties of various (per)¯uoroelastomers.
10.2. Fluid and chemical resistance
Chemical attack results in the swelling of the elastomer (regarded usually as a reversible event).
Swelling up to ca. 10% can bene®cially increase the sealing force produced by an elastomeric gasket, but
too much swell can cause the seal to become damaged leading to a premature failure. Chemical attack
can degrade the material and this should be avoided at all costs.
As a class, ¯uoroelastomers are notably resistant to swelling in aliphatic, aromatic and chlorinated
hydrocarbons, fuels, oils and many other organic liquids. They display good to excellent resistance to
chemical attack, ¯ame propagation, oxidation, ozone and weathering. Resistance generally increases
with increasing the ¯uorine content and FKM w elastomers are unaffected by almost all solvents and
reagents such as alcohols, ketones, esters, amines and other polar solvents which considerably swell, or
in the case of amines react with other types of elastomers (Table 8).
Peroxide-curable types of Viton w were originally invented to offer higher performance properties than
could be obtained by standard grades of ¯uoroelastomers. The range of properties that these types can
achieve is very exciting. In addition, peroxide-curable types have always offered higher tensile strengths
and shorter cure cycles [463]. Compared with others of their group, peroxide-cured type elastomers have
considerably greater resistances to swelling in organic media and to degradation in hot aqueous media.
One particularly outstanding ¯uoropolymer used in elastomeric applications is that prepared from
TFE and PAVE, and particularly PMVE (Table 9). To facilitate the crosslinking of these copolymers
(FFKM w) essential to achieve better elastomeric properties, a small percentage of termonomer is
generally incorporated, such as a cyano- or nitrile-containing ¯uoroole®ns [273,303]. These cyano-
per¯uoroelastomers exhibit outstanding thermal and oxidative stabilities. Fluoroelastomers having
iodine cure sites do not have a high concentration of ionic end-groups, such as carboxylic or sulfonic
acid moieties, which are introduced from the initiating system. Conventional chain transfer agents can be
used to lower the concentration of the ionic end-groups and also to lower the polymer viscosity [303].
The main properties of uncured TFE/PMVE elastomers and ¯uid resistance of vulcanizates at 258C
have been discussed by Barney et al. [267]. Indeed, the copolymer is totally soluble in a variety of highly
¯uorinated liquids, including per¯uorokerosene, per¯uorodiisopropyl ketone, per¯uorotributyl-amine,
etc. It is essentially completely resistant (less than 2% swelling) to most other liquids, including strong
aqueous bases, concentrated nitric or sulfuric acids, hydrazine, alcohols, ketones, esters, acids, amines,
amides, ethers, aliphatic or aromatic hydrocarbons and partially chlorinated derivatives. The polymer
wets Te¯on w and Te¯on w FEP readily.
The cured polymer is slightly attacked at temperatures around 2508C by di- and polyamines acting as
reducing agents.
However, there are some distinct differences in the swelling under extreme conditions for FKM items
obtained with different cure systems. The bisphenol-cured pieces swell most in glacial acetic acid and
water and least in ethylene diamine. The peroxide-cured stocks swell least in high-temperature water
under pressure. Thus, one can choose the system that gives the optimum properties for a practical
application. All FKM w swell to some degree in chloro¯uorocarbons or ¯uorocarbon solvents [24].
Fig. 4. Diagram of ¯uoroelastomer item-distribution.
Up to 2108C, ¯uoroelastomers remain serviceable inde®nitely offering excellent resistance in most

solvents and chemicals (Table 8). New ¯uoroelastomers offer easily processable and low compression
set high-¯uorine terpolymers, contradicting the previous statement that the higher the ¯uorine content,
the better the chemical resistance at the expense of processability and compression set. Heat and oil
resistances are obviously to be considered together with other properties such as tensile or compression
set [23].
Perlast w is affected by strong oxidizing and reducing agents. Boiling tertiary amines and molten alkali
metals (Li, K, Na, etc.) should be avoided as it is for all ¯uorinated polymers.
Extremely strong oxidizing agents such as ¯uorine gas and related compounds can produce volatile
mixtures after reacting with ¯uoropolymers. Chemicals which would cause a large volume change
should be avoided (they include HCFC, CFC, ¯uorinated oils, CTFE oils). Such a change is not
necessarily fatal to the product: the effect is one of swell rather than degradation. Strong oxidizing
agents such as fuming nitric acid will attack carbon black: a non-black ®ller should be used in such
environments [222].
Both Perlast w and other FFKM w per¯uoroelastomers performed quite satisfactorily over this extended
test and the values of three physical measurements taken remain within narrow bands. In contrast, the
FKM w swells rapidly before the 336 h interval [222].
The major advantages of TFE/P elastomers (A¯as w) compared to FKM w ¯uoroelastomers are a better
chemical resistance to automotive oils and lubricants combined with a more consistent response to
different types and brands of these ¯uids [529]. It maintains the good high-temperature resistance for
which FKM ¯uoroelastomers are noted. Engine oils, transmission ¯uids and gear lubricants are complex
formulations of base stocks and additive packages. A new type of engine oil designated by the SG term
was introduced in 1988 and nowadays there are various oil formulations that meet these speci®cations.
Table 10
Mechanical properties of different types of ¯uoroelastomer [15,221]
Property Fluoroelastomers
FFKM w FKM w TFE/P Fluorosilicone
100% Modulus (MPa) 6.2±13.1 2.1±15.2 2.5±3.5 1.0±6.1

Tensile strength (MPa) 14.5±16.8 9.0±18.6 18.0±20.0 6.2±8.6
Elongation (%) 120±240 100±500 250±350 100±500
Compression set (%) 35±50 $ 10 45±50 60
70 h, 2008C
Hardness (Shore A) 70±95 90±95 65±75 50±75
Brittle temp. (8C) 2 40 to 230 2 59 to 218 2 40 2 66
Accordingly, elastomeric parts have to be exposed to many different oil and lubricant chemical envir-
onments. Interestingly, TFE/P elastomers are resistant to a wide variety of engine oils and lubricants.
In contrast to the FKM w elastomers, TFE/P ones are not dehydro¯uorinated in engine oils and they
maintain stable properties after exposure to a wide variety of engine oils.
Mechanical properties after exposure to engine oils are much better (Table 10). Various oils have little
impact on TFE/P with elongation changes varying from 210.5 to 25.0%. In contrast, FKM w elongation
changes vary from 241.3 to 275.2% [529]. There is no evidence of surface attack on the TFE/P test
specimens but FKM w shows evidence of surface crazing or cracking. The same trend was observed
during chemical resistance. The changes in tensile strength and volume swell are that the volume swell
of A¯as w reach an equilibrium very quickly and is stable over the duration of the test.
TFE/P exhibits very good transmission ¯uid resistance and also consistent resistance to the various
automatic transmission ¯uids [529]. Peroxide-curable ¯uoroelastomer FKM w 5927 exhibits the superior
¯uid-resistance as Viton w GF and low-temperature performance with improved processability [550].
FKM w 5958 shows excellent low-temperature ¯exibility and compression set resistance maintaining the
outstanding ¯uid-resistance of the solvent-resistance-type ¯uoroelastomers.
Broad and extensive research has been realized since the time of development of standard ¯uoroe-
lastomers and their crosslinking to solve processing problems and to obtain easy processing products for
high performances requiring a higher chemical stability against aggressive oils, together with optimum
mechanical properties and aging at high temperatures. For the ªcriticalº injection molding technology, a
new type of Techno¯on w P 189 N has been commercialized [259].
A new family of improved base-resistant VDF ¯uorocarbon elastomers has been developed by
Ausimont as a commercial product called Techno¯on w BRX 915 N. Heat aging at 2758C is in compar-
ison with a standard peroxide-curable VDF ¯uorocarbon elastomer (e.g. Techno¯on w P 819 N). The new
grade has a higher resistance to high-temperature aging in a basic engine coolant [89].
A ¯uoroelastomer endowed with high resistance to polar solvents and to bases, excellent compression
set at high temperatures, low glass transition temperature and good processability was synthesized from
suitable ratio of TFE, PAVE and VDF, the last one being 10±20 mol% in the terpolymer. PAVEs are
preferably chosen among the ®rst three homologs (C1 ±C3). Such ¯uoroelastomers are particularly
suitable for the manufacture of sealing elements for plants intended to methyl tert-butyl ether production
[261].
Table 11
Fluoroelastomers: trademarks and properties
Trademark Comonomers in copolymer %F Tg (8C) Advantages/drawbacks
Viton w Good chemical resistance at

high T
Fluorel w VDF/HFP 64 218 Resistance to oxidation,
solvents, ¯ames
Tecno¯on w May swell
Dai-el w VDF/HFP/TFE 70 27, 213, 221 High thermostability, better
resistance to swelling
FKM w VDF/HFP/TFE with CSM 67 216 Better mechanical properties
VDF/HFP/TFE/E(5%) Variable E protects from alkaly attack
VDF/PAVE Variable 240 Resistance to oxidative
attack
Tecno¯on w VDF/HCFyCFCF3 Variable Heat resistance, as above and
to solvents
VDF/TFE/HCFyCFCF3 62±70
Kel F w VDF/CTFE Variable 215 Vulcanization: better heat
and chemical resistance
Atlas w TFE/P 54±57 Chemical, heat and pressure
resistance
10.3. Thermal resistance
Fluoroelastomers have outstanding resistance to heat compared with other elastomers. VDF-based
¯uoroelastomers and ¯uorosilicones are capable of long-term service in dry heat at 2008C, while FKM w
elastomers are stable for many months at 2608C (and Kalrez w for continuous use at 3168C). The
¯uorophosphazenes have a lower long-term service temperature (,1758C). Of course, all are capable
of useful short-term service at higher temperatures (Table 9) [15,22,23].
The use at low temperatures obviously depends on the application. Service in static applications is
often satisfactory at temperatures appreciably lower than those used in dynamic applications. The
¯uorosilicones and ¯uorophosphazenes (PNF w) have lower Tgs and higher ¯exibility than those of
FKM w rubber (their Tgs are in the range of 210 to 2308C) while VDF/TFE/PMVE have a wide
temperature operating interval [15,23,24].
Actually, Van Cleeff [23] has interestingly reviewed the situation of the Tgs of Viton w elastomers
versus the hydrogen content. From those containing TFE, VDF and PMVE base units, the author showed
that the higher the H mol%, the lower the Tg (the lowest Tg was observed for Viton w GLT containing 1.7
H mol%, Tg 2298C: From the terpolymers involving TFE, VDF and HFP, a similar tendency as
above was noted. For example, the Tg of Viton w A is 2178C (H mol% 1.9) while that of Viton w B-70
is 2208C (H mol% 1.8). Obviously, for the same H content, the Tgs of the ®rst series are always lower
than those of the second one.
Cured per¯uoroelastomers show exceptional thermal stability and are differentiated by the robustness
of their crosslinks. The per¯uoroelastomers with pendent nitrile groups as cure sites retain their proper-
ties in the best way after they are exposed to high temperatures. The triazine crosslinks are stable enough
to show little or no change from the original post-cure properties after 18 days at 2888C in air. Even after
short exposure to 3168C useful properties are maintained [221].
Per¯uoroelastomers cured with bisphenols are less stable to heat and after 20 days at 2808C in air the
100% modulus is reduced by about 25% and the tensile strength by about 15%, while the elongation is
increased by about 120%. The peroxide-curable polymers are less thermally stable, starting to loose
properties signi®cantly after few days at about 2208C in air. The radiation-cured parts still have lower
thermal resistance, limiting their use to around 2008C.
The differences in thermal resistance are attributed to curing chemistry and to the stability of the
crosslink structures, since all of the polymers are per¯uoroelastomers and have almost the same back-
bone structure (Table 11). Thus, the triazine structure is the most thermally stable. The bisphenol
crosslinks are also thermally stable, but a little inferior to those of the triazines [15,221].
The crosslink structure generated during a peroxide-cure is related to the structure of the coagent
being used. Since the coagents have a hydrocarbon skeleton, their thermal stability in air is limited. The
irradiation-cured parts appear to have a carbon±carbon crosslink structure and are expected to have good
thermal resistance. However, during irradiation, some chain scissions occur, and result in the formation
of carboxylic acids, which lowers the thermal stability of the crosslinked parts [23,24].
The advantageous low-temperature properties of Perlast w have important implications for sealing
performance because the wide majority of applications for per¯uoroelastomers exist below 2008C [222]
(Fig. 4).
10.4. Mechanical properties
The tensile properties of the ¯uoroelastomers are generally satisfactory; TFE/PMVE and TFE/P
having the highest ones while ¯uorosilicones and ¯uorophosphazenes show the lowest tensile strength
at room temperature. The polymers with inorganic backbones do retain a higher proportion of their
tensile properties at higher temperatures. Resistance to compression set is an important property of
¯uoroelastomers because the largest end-use concerns seals (particularly O-rings) [15±24]. The intro-
duction of bisphenol-curing system considerably improves the compression set resistance. VDF- and
TFE-based elastomers give materials with compression sets as low as 10±15% after 70 h at 2008C in air.
TFE/P elastomers have poor resistance to compression set and FFKM w copolymers show slow recovery
from compression at temperatures below about 1508C [15].
The physical properties of the chemically cured parts compare well with each other and typical values
are shown in Table 10. Some formulations are better than others, and pronounced differences are obvious
when the testing conditions change. Items cured by high-energy irradiation have similar properties as the
heat-cured articles, except for hardness and tensile properties. The absence of reinforcing ®llers in these
objects is the cause of lower stress at 100% elongation (3 MPa), tensile strength (10 MPa) and hardness
Shore A (65) and higher values in elongation at break (250%) [24,476].
A new type of ¯uoroelastomer, Techno¯on w P 819N [89,261], exhibits a mixed hydroxylic/peroxide
network. The reducing of the amount of onium salt (decreasing the amount of unsaturations) is compen-
sated by peroxide curing of brominated chain ends by synthesizing the copolymer in the presence of a
brominated chain transfer agent. The processing problem of peroxide-cured ¯uoroelastomers has been
overcome by introduction of ¯uorinated substances. The other possibility is bromine or iodine-polymer
development using ªdi-iodo techniquesº of Tatemoto [100±103]. Polymers having iodine-terminated
chain ends cure very ef®ciently with peroxides giving good processing properties in terms of fast cure
rate and easy moldability. However, when resistance to heat is considered, the network obtained with
diiodo-terminated chain ends appears to be considerably less stable. Techno¯on w P 819 N is an excellent
elastomer for injection molding together with higher resistance to aggressive oils [261].
Per¯uoroelastomers (such as those containing TFE/PMVE base units) having iodine cure sites exhibit
outstanding thermal and oxidative stability [463].
Viton w GF 3000 is the improved processing and lower viscosity version of Viton w GF [463]. It is
similar to the latter (containing VDF/HFP/TFE units) but, except for bromine CSM, it incorporates
additional enhanced proprietary brought by the CS moiety. Viton w GF 300 exhibits lower compounded
viscosity and faster cure rate. At the same time, the low-temperature properties are similar to those of
Viton w GF. Elongation increasing at 200 and 2508C are worse than that of Viton w GF but they have the
same ¯uid resistance (automotive ¯uids, water, steam and acids). Viton w GF 205 NP is the no post-cure
Viton w type with very good physical properties. Viton w GF 205 NP has a faster cure rate than either
Viton w A 401 C or Viton w GBL 200 with similar scorch safety as that of Viton w GBL 200. Compression
set values of no post-cure compared to standard bisphenol-cure type (Viton w A 401 C) are better.
Original physical properties, such as tensile strength and elongation without post-cure are good but
heat aging results are not as good as those of standard Viton w. The ¯uid resistance data show that the
Viton w GF 205 NP acts as much as a 70% ¯uorined material [463]. Viton w GBL 205 LF is a VDF/HFP/
TFE terpolymer and contains a proprietary acid acceptor system so that metal oxides are neither required
nor recommended in the formulations.
Viton w GBL 205 LF has excellent resistance to acids without the need to use lead. Regarding all other
physico-chemical and rheological properties, it behaves similarly as a peroxide-curable Viton w B-type.
Interestingly, this product is signi®cant for the development of rubber processors and it provides an
environmentally friendly method to obtain excellent resistance to steam and acids [463].
11. Applications of ¯uoroelastomers
Fluoroelastomers were originally developed for use as fuel tank hatch and joint sealants, fuel vapour
seals and O-rings for hydraulic systems in aircraft and aerospace applications. Fluoroelastomers are now
widely used in the industry as O-rings, V-rings, gaskets and other types of static and dynamic seal, as
diaphragms, valve seals, hoses, coated cloth, shaft seals [496], expansion joints, etc. They are also used
in cars as O-rings for fuel and shaft seals and other components of fuel and transmission systems [15,19±
24,409].
Commercial applications of ¯uoroelastomers re¯ect their rather special combination of properties:
excellent resistance to heat, ¯uids, oxidizing media combined with good physical properties.
Today, VDF/HFP and VDF/HFP/TFE polymers are produced and marketed internationally by differ-
ent companies such as Du Pont Dow Elastomers (Viton w), Ausimont (Techno¯on w), Dyneon (Fluorel w)
and Daikin (Daiel w) (Table 2). Lower capability is attributed to products from other countries: Russia
(SKF w 26, SKF w 32, SKF w 260), China and Japan (Nippon Mektron and Asahi) [22] (Table 11).
The main types of ¯uoroelastomer part used are shown in Fig. 4.
The main consumer (60%) of the ¯uoroelastomer parts is the automotive industry
[463,467,538,547,551]. In most sealing applications, an elastomeric seal is the most susceptible compo-
nent to the seal assembly. Several factors are considered when the elastomers have to be chosen for seal:
operating temperature, thermal cycling, pressure range, seal environmental, ¯uid type, etc. Oxygenates
used in gasoline (e.g. methyl tert-butyl ether, MTBE) required higher-performance elastomeric materi-
als to prevent equipment leakage, equipment failure and costly downtime [261].
In MTBE environments, FFKM w behaves considerably better than conventional ¯uoroelastomers do,
leading to a longer seal life and improved protection against seal failure.
The chemical and petrochemical industries also represent a promising market (10%) for ¯uoroelas-
tomer items. These industries expose elastomers to a wide variety of chemical reagents and operating
conditions [15,17,19±24].
In many applications, chemical plants must retro®t existing values or replace them with new valves
that conform to the more stringent standards. The chemical resistance provided by a FFKM w combined
with the lighter sealing load results in longer service life and reduced fugitive emissions (over 33% of all
air-toxic volatiles) in different valves of chemical industry using now PTFE sealings.
Energy-consuming industries for control systems require ¯uoroelastomers for joints and lining resis-
tant to corrosive materials.
Fluoroelastomers and especially FFKM w play an important role in sealing applications in both
commercial and military aircraft industries (10%).
Aerospace propellant systems often utilize very aggressive fuels and oxidizers which are incompatible
with all currently available elastomers, including ¯uoroelastomers. FFKM w are often used in these
systems due to their oxidative stability and compatibility with both oxidizers and hydrazine-type fuels.
Fire-resistant lubricants containing phosphate esters and lubrication oils-containing amines are both
interesting applications where the use of FFKM w greatly extends seal life.
FFKM w are the most suitable materials available for use in semiconductor processing equipment
[552,553]. In these applications, the elastomer comes in direct contact with dry process chemicals and
reactive plasmas. The elastomer is typically exposed to aggressive wet chemical environments such as
sulfuric acid/hydrogen peroxide or ammonium hydroxide/hydrogen peroxide/ultra pure deionized water
mixtures. In such applications, limiting the contaminants to only parts per billion is crucial. The use of
FFKM w that combines chemical resistance and minimum release of contaminants becomes the most cost
effective sealing material for the semiconductor chip fabrication process [222,554].
Although discovered more than 20 years ago, per¯uoroelastomers represent a production of only a
few thousand kilograms a year. However, they are growing at a fast pace in terms of applications and
introduction of new composition to meet industrial needs. Per¯uoroelastomers represent less than 1% of
the total ¯uoroelastomer ®eld, dominated by VDF-base copolymers.
Most of the current research efforts are directed to improve the properties of ¯uoroelastomers and their
processability. It is expected that new ¯uoropolymeric materials and new curing chemistry will be
developed in the future due to continued escalation at severe service conditions and improvements in
broad temperature damping characteristics and low-temperature resilience [21]. Blends of ¯uoroelasto-
mers with other polymers and recyclability features will also contribute to their continuing success in
many engineering and aggressive service environments.
12. Conclusions
Among ¯uoropolymers, elastomers, which represent a more recent generation, have shown relevant
properties. In spite of the fact that they are highly priced, they are useful since they exhibit poor swelling
in oils, hydrocarbons, solvents, but are resistant to heat, aging, concentrated acids and alkalies and have
useful mechanical and compression set properties. Hence, they open up prospects of new applications in
numerous ®elds: oil, automotive, chemical, aerospace and aeronautic industries.
Thus, most companies involved in ¯uorine chemistry devote funds and research to challenging
products to which ¯uoroelastomers belong to. A wide range of ¯uoroelastomers are commercially
available or synthesized in a small scale; basically, they can fall into three main categories: (i) ¯uor-
ocarbons containing mainly carbon, ¯uorine and to a less extent hydrogen and oxygen atoms (most of
them are produced from the radical copolymerization of VDF or TFE or from the terpolymerization
involving both of them). However, maintaining their outstanding properties at low temperature remains
a great challenge that (ii) ¯uorosilicones have overcome. (iii) concerns the ¯uorinated polyphosphazenes
endowed with excellent ®re resistance.
The synthesis of ¯uorocarbon elastomers by direct radical co- or terpolymerization of ¯uoroole®ns has
been further proved to be a versatile way that offers many opportunities for obtaining a wide range of
¯uoropolymers.
The production and demand of ¯uorinated elastomers are having an increasing market for novel
applications: seals and O-rings inert to oils and hostile environments.
However, to enhance their properties, curing reactions are required. Usually, they occur in the
presence of various reactants, or a mixture of reagents (e.g. bisphenols, polyamines, peroxides/TAIC)
at rather high temperatures.
Hence, a new generation of more easily crosslinkable ¯uoroelastomers has been achieved from novel
reactive monomers which exhibit halogen atoms (bromine or iodine, mainly) or functional groups (e.g.
hydroxy, carboxy, mercaptan). Although such monomers are the most expensive counterpart in the
preparation of the ¯uoroelastomers, generally just 1±5% of them is required in the copolymer to
allow it to be crosslinked. Thus, their reactivity in co- or terpolymerization has to be taken into account
to utilize them fully while it is sometimes neglected or not regarded as a crucial parameter.
Thus, further work in synthesizing more reactive co-monomers with adequate function and kinetic
factors should be expected to enable one to go to the next generation of ¯uoroelastomers.
The availability of this new class of ¯uoropolymers should open many interesting opportunities for
exploiting the unique properties of these elastomers in many uses.
This offers additional chances to a technology that already forms the basis of the commercial produc-
tion of classes of chemicals which are among the most advanced and successful products in ¯uorine
chemistry. Such new targets are real challenges and should attract the interest of many academic and
industrial researchers in this fascinating area.
Acknowledgements
The authors thank the Centre National de la Recherche Scienti®que for an invited Professor/
Researcher position (ªPoste Rougeº) at the Ecole Nationale SupeÂrieure de Chimie de Montpellier (to
G.K.).
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Fluoroelastomers - Synthesis, Properties and Applications

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Prog. Polym. Sci.

Fluoroelastomers: synthesis, properties and applications

* Corresponding author. Tel.: 133-4-67-14-4368; fax: 133-4-67-14-7220.

2.2.2. Vinylidene ¯uoride (VDF orVF2) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112

7.5. Post-curing of ¯uoroelastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156

1st Generation: Fluorinated homopolymers

1934±1938 PCTFE (C2F3Cl), PTFE (C2F4)

2nd Generation: Fluorinated copolymers

1950±1960 VDF/CTFE (C2H2F2 ±C2F3Cl)

3rd Generation: Fluorinated functional polymers

1980 Ion exchange membranes; room temperature crosslinkable paints

2.1. Combination of ¯uoroalkenes

B. AmeÂduri et al. / Prog. Polym. Sci. 26 (2001) 105±187

HFP PMVE CTFE P HPFP

VDF Daiel w 801 (Daikin) ± Kel F w (Dyneon) ± Tecno¯on w SL (Ausimont)

2.2. Synthesis of ¯uoroalkenes

2.2.1. Vinyl ¯uoride

2.2.2. Vinylidene ¯uoride (VDF or VF2)

2.2.3. Chlorotri¯uoroethylene (CTFE)

2.2.4. Tetra¯ouroethylene (TFE) and hexa¯uoropropylene (HFP)

2.2.6. Fluorinated styrenic monomers

2.3. Polymerization of ¯uoroalkenes

H2 O2 + n VDF + p HFP HO (VDF)x (HFP) G

3.2. Various kinds of ¯uorinated copolymer

3.2.1. Fluorinated block copolymers

1 + c VDF I(VDF) (VDF) (HFP) R’ (VDF) I

2 + p H2C = CH ATRP Br(Sty)x RF (VDF) n (Sty) y Br

CH2 OC2 H4 C8 F17

(Sty)p (CH2 CH) n

(Sty)p (CH2 CH) (Sty)p (CH2 CH)n

(Sty)p (CH2 CH) n (Sty)p (CH2 CH) n

CH2 SCN(Et)2 + H2C=C(CH3)CO2C2H4N(Et)2 ∆ or hυ CH2(M1)nSCN(Et)2

5 1 H2 CyCH±CO2 CH2 C7 F15 ! poly M1 -b-P FOA

By atom transfer radical polymerization, various poly(M1)-b-PFOMA were obtained, M representing

3.2.2. Fluorinated graft copolymers

3.2.3. Fluorinated alternating copolymers

3.3. Kinetics of copolymerization

3.3.1. Terminal model

Monomer a Comonomer b Properties c References

CTFE E Cryst. [125]

dM1  M1  r1 M1  1 M2 

r1  k11 =k12 and r2  k22 =k21

3.3.2. Penultimate model

3.3.3. Complex participation model in the acceptor donor copolymerization

3.3.4. Other copolymerization models

3.3.5. Q and e parameters and other concepts

H2CyCHCF3 0.42 0.130 [174]

F2CyCF±CFyCF2 (cont.) 4.09 0.047 [183]

4. Fluoroelastomers from TFE

4.2. Fluoroelastomers from TFE and propylene

Radiation-induced emulsion copolymerization of TFE with P has been studied extensively by

4.3. TFE-based ¯uoroelastomers containing ethylene (E)

4.4. Thermoplastic ¯uoroelastomers

4.5. Per¯uoroelastomers from TFE and PAVE monomers

(CF 2 CF 2 ) (CF 2 CF) (CF 2 CF) z

4.5.1. Synthesis of comonomers

SO3 CF2 CF2

∆ CFOCF2 CF2 CF2 SO2 F

Other synthetic methods have been achieved on a research scale.

FSO2 CF2 COF 1 KF ! FSO2 CF2 CF2 OK ! FSO2 C2 F4 OCF2 CFyCF2

5 1 H2 CyCH±CO2 CH2 C7 F15 ! poly M1 -b-P FOA

dM1 M1 r1 M1 1 M2

r1 k11 =k12 and r2 k22 =k21

VDF 1 F2 CyCFOCF2 CF CF3 OC3 F7 ! poly VDF-co-PAAVE

CF3 CF2 OCF2 CF CF3 n F n , 10; 300

CF3 OCF2 CF CF3 Op CF2 On CF3 n , 7000

±O±CF CF3 CF2 n ± n , 16; 600

HOCH2 OC2 F4 p OCF2 CF CF3 q OCF2 r CH2 OH Fomblinw Z-diol

±NyP Cl2 ± 1 R1 CH2 ONa ! ±NyP OCH2 R1 2 n ±;

R4 P1 OH2 1 HO±Ar±OH ! R4 P12 OAr±OH 1 H2 O 4

R4 P12 OArOH 1 F±Polym ! R4 P1 F2 1 Polym±OArOH 5