3 Fluoroelastomer Monomers

3.1

Introduction

range of monomer mixtures is a major consideration

for fluoroelastomers producers.

The major fluorinated monomers for fluoroelastomers are the same as those used for fluoroplastics. Production volumes of fluoroplastics, and thus
of their monomers, are much higher than the volumes of fluoroelastomers. This allows the supply of
modest amounts of monomers for fluoroelastomers
at reasonable cost. Most producers of fluoroelastomers are also producers of fluoroplastics, or allied
with these suppliers. Vinylidene fluoride (VDF) accounts for about half the volume of monomers used
for fluoroelastomers. Tetrafluoroethylene (TFE) and
hexafluoropropylene (HFP) are the other main fluorinated monomers in fluoroelastomers. Perfluoro(methyl vinyl ether) (PMVE), used in specialty
fluoroelastomers, is not used in fluoroplastics, but
can be made in facilities used for manufacturing the
perfluoro(alkyl vinyl ethers) (PEVE and PPVE),
monomers used in fluoroplastics. A number of curesite monomers and fluorinated chain-transfer agents
are also made in low volumes for specialty fluoroelastomers. Safe handling of these monomers and a wide

3.2

Vinylidene Fluoride (VDF)

Vinylidene fluoride is incorporated at levels of

50 to 80 mole % (30 to 65 weight percent) in the
major family of copolymers with hexafluoropropylene and tetrafluoroethylene, and at similar levels in
the specialty family of copolymers with
perfluoro(methyl vinyl ether) and tetrafluoroethylene. In both families, VDF contributes to low glass
transition temperatures to allow good elastomeric
behavior. Long sequences of VDF units would lead
to undesired crystallinity.

3.2.1

VDF Properties

Vinylidene fluoride (VDF), CH2=CF2, is flammable and is a gas at room temperature. Physical
properties of vinylidene fluoride are presented in
Table 3.1. It is colorless and almost odorless and

Table 3.1 Properties of Vinylidene Fluoride[1]

Property

Value

Molecular weight

64.038

Boiling point, C

-84

Freezing point, C

-144

Vapor pressure at 21C, kPa

3,683

Critical pressure, MPa

4.434

Critical temperature, C

30.1

Critical density, kg/m3

417

Heat of formation at 25C, kJ/mole

-345.2

Heat of polymerization at 25C, kJ/mole

-474.2

Explosive limits, vol % in air

5.8-20.3

Solubility in water, cm3/100 g at 25C at 10 kPa

6.3

Activation energy of polymerization, Eo, kJ/mole

161

26

FLUOROELASTOMERS HANDBOOK

boils at 84C. Vinylidene fluoride can form explosive mixtures with air. Polymerization of this gas is
highly exothermic and takes place above its critical
temperature and pressure. Propagation rates of VDF
with itself and other fluorinated monomers are high,
facilitating high production rates of VDF-containing
fluoroelastomers.

3.2.2

VDF Synthesis

There are numerous ways to prepare vinylidene

fluoride (VDF) which is the main monomer for polyvinylidene fluoride homopolymers and copolymers.
A number of these methods are based on dehydrohalogenation of halohydrocarbons. Examples include
dehydrobromination of 1-bromo-1,1-difluoroethane[2]
or dehydrofluorination of 1,1,1-trifluoroethane.[3][4]
Two methods, including the popular commercial technique for VDF production, are described here.
Conversion of 1,1,1-trifluoroethane[3] begins by
passing this gas through a platinum-lined Inconel tube,
which is heated to 1,200C. Contact time is about
0.01 seconds. The exit gases are passed through a
sodium fluoride bed to remove the hydrofluoric acid
and are then collected in a liquid nitrogen trap. Vinylidene fluoride (boiling point 84C) is separated
by low temperature distillation. Unreacted trifluoroethane is removed at 47.5C and is recycled. The
effect of temperature and contact time is illustrated
in Table 3.2, clearly favoring the high temperature
process.
Table 3.2 Effects of Contact Time and Temperature
on Vinylidene Fluoride Yield from Dehydrofluorination
of 1,1,1-Trifluoroethane[3]

Variable

Case 1

Case 2

Temperature, C

1,200

800

Contact time, s

0.01

4.4

Space velocity, 1/h

9,700

200

Total conversion, mole %

75.4

76

Conversion to vinylidene
fluoride, mole %

74

66

Vinylidene fluoride yield, %

98.1

86.5

By-products yield, %

1.9

13.5

CH3CF3 CH2=CF2 + HF
The commercial method begins with hydrofluorination of acetylene followed by chlorination,[5]
by hydrofluorination of trichloroethane,[6] or by
hydrofluorination of vinylidene chloride.[7] In each
case the final product, 1-chloro-1,1-difluoroethane,
is stripped of a molecule of hydrochloric acid to yield
VDF. The following one-step reaction scheme is
shown for vinylidene chloride as the starting ingredient:
CH2=CCl2 + 2HF CH3CClF2 + HCl
CH3CClF2 CH2=CF2 + HCl
A mixture of vinylidene chloride (VC2) and hydrofluoric acid is passed through a heated catalyst
bed. The catalyst is prepared by heating CrCl36H2O
under vacuum to 300C until it changes color from
dark green to a solid violet throughout the porous
mass. In this operation, crystallization water is removed (35% weight loss). The cooled mass is comminuted and screened into particles of 25 mm diameter that are loaded into a cylindrical reactor and
heated to the reaction temperature (250C350C).
The resulting gases are condensed and vinylidene
fluoride (boiling point 84C) is separated by low
temperature distillation. Table 3.3 provides yield information for a few different reaction conditions. It
appears that nearly a 100% yield can be achieved in
Case 3.
In another one-step process,[8] a mixture of vinylidene chloride and hydrofluoric acid is heated to
400C700C in the presence of oxygen and a
catalyst. Aluminum fluoride, alone or in combination
with a transition metal such as cobalt, chromium,
nickel, zinc or their combinations, is the catalyst for
the reaction.

3.3

Tetrafluoroethylene (TFE)

Tetrafluoroethylene is incorporated at up to 30
mole % in VDF-containing fluoroelastomers. Partial replacement of VDF with TFE in these copolymers results in higher fluorine content and thus
greater fluid resistance. In perfluoroelastomers and
in fluoroelastomers containing olefins, TFE is incorporated at higher levels, some 40 to 70 mole %.

3 FLUOROELASTOMER MONOMERS

27

Table 3.3 Effect of Contact Time and Temperature on Vinylidene Fluoride Yield from Hydrofluorination of Vinyl
Chloride[7]

Variable

Case 1

Case 2

Case 3

Case 4

Temperature, C

345

330

290

250

Space velocity, 1/hr

300

155

200

200

Mole ratio VC2:HF

1:4.7

1:2.7

1:5.3

1:4.7

Vinylidene fluoride yield, %

97.0

96.5

99.8

95.0

3.3.1

TFE Properties

Table 3.4 lists the properties of tetrafluoroethylene. It is a colorless, odorless, tasteless, nontoxic
gas that boils at 76.3C and freezes at 142.5C.
Critical temperature and pressure of tetrafluoroethylene are 33.3C and 3.92 MPa. TFE is stored as a
liquid; vapor pressure at 20C is 1 MPa. Its heat of
formation is reported to be 151.9 kcal/mole. Polymerization of tetrafluoroethylene is highly exothermic and generates 41.12 kcal/mole heat. The extent of the exothermic nature of TFE polymerization
can be seen when it is compared with the polymerization of vinyl chloride and styrene, which have heats
of polymerization of 2326 and 16.7 kcal/mole, respectively.
A complete description of explosive hazards of
tetrafluoroethylene can be found in Ref.10. Safe storage of TFE requires its oxygen content to be less
than 20 ppm. A great deal of research has been
devoted to safe handling of tetrafluoroethylene. [11]
Temperature and pressure should be controlled during its storage. Increasing temperature, particularly
at high pressures, can initiate deflagration in the absence of air. In the presence of air or oxygen, TFE
forms explosive mixtures. Detonation of a mixture
of tetrafluoroethylene and oxygen can increase the
maximum pressure to 100 times the initial pressure.[12]
Tetrafluoroethylene undergoes free radical addition reactions typical of other olefins. It readily adds
Br2, Cl2, and I2, halogen halides IBr and ICl, and
nitrosyl halides such as NOCl and NOBr.[13][14] Addition reactions of chlorofluoromethanes and
chloromethanes in presence of catalysts like aluminum chloride have been reported.[15] A variety of

other compounds such as alcohols, primary amines,

and ammonia can be reacted with tetrafluoroethylene to prepare tetrafluoroethers (HCF2CF 2OR),
difluoroacetamides (HCF2CONHR), and substituted
triazines.[16] Oxygen can be added to TFE to produce polymeric peroxide[17] or tetrafluoroethylene
epoxide.[18] In the absence of hydrogen, sodium salts
of alcohols will react with TFE to yield trifluorovinylethers (ROCF=CF2) which can be homo- and
copolymerized.

3.3.2

TFE Synthesis

It is difficult to establish exactly the first successful synthesis of tetrafluoroethylene. Publications

in the 1890s report a variety of attempts to synthesize TFE by direct reaction of fluorine with carbon,
fluorine with chloromethanes, and tetrachloroethylene with silver fluoride.[19][22] The data presented
are insufficient to determine that these efforts actually lead to TFE. Humiston[23] reported the first documented preparation of TFE in 1919 which has been
disputed because of erroneous property data.
The first reliable and complete description of synthesis was published in 1933 by Ruff and
Bretschneider,[24] who prepared TFE from decomposition of tetrafluoromethane in an electric arc.
Separation of TFE from the pyrolysis products was
accomplished by bromination followed by dehalogenation with zinc. Numerous other papers have
reported synthesis of tetrafluoroethylene. The works
that report commercially significant techniques for TFE
preparation list fluorspar (CaF2 ), hydrofluoric acid,
and chloroform as the starting ingredients.[25][32]
The reaction scheme is shown below:

28

FLUOROELASTOMERS HANDBOOK

Table 3.4 Properties of Tetrafluoroethylene[9]

Property

Value

Molecular weight

100.02

Boiling point at 101.3 kPa, C

76.3

Freezing point, C

142.5

Liquid density vs. temperature (C), g/mL

100 < t <-40
40 < t < 8
8 < t < 30

1.202 0.0041t
1.1507 0.0069t 0.000037t2
1.1325 0.0029t 0.00025t2

Vapor pressure at T K, kPa

196.85 < T < 273.15
273.15 < T < 306.45

log10PkPa =6.4593-875.14/T
log10PkPa =6.4289-866.84/T

Critical temperature, C

33.3

Critical pressure, MPa

3.92

Critical density, g/mL

0.58

Dielectric constant at 28C

at 101.3 kPa
at 858 kPa

1.0017
1.015
15.5

Thermal conductivity at 30C, mW/(mK)

Heat of formation for ideal gas at 25C, H,kJ/mole

635.5

Heat of polymerization to solid polymer at 25C, H, kJ/mole

172.0

Flammability limits in air at 101.3 kPa,vol%

14-43

1. HF preparation:
CaF2 + H2SO4 2 HF + CaSO4
2. Chloroform preparation:
CH4 + 3 Cl2 CHCl3 + 3 HCl
3. Chlorodifluoromethane preparation:
CHCl3 + 2 HF CHClF2 + 2 HCl (SbF3 catalyst)
4. TFE synthesis:
2 CHClF2 CF2=CF2 + 2 HCl (pyrolysis)
A few other side compounds are also produced
during pyrolysis including hexafluoropropylene,
perfluorocyclobutane and octafluoroisobutylene, 1chloro-1,1,2,2-tetrafluoroethane, 2-chloro-1,1,1,2,3,3hexafluoropropane, and a small amount of highly toxic
perfluoroisobutylene.

Sherratt[10] has provided a detailed description

of preparation of TFE. The overall yield of TFE production depends on the pyrolysis reaction. It proceeds to yield better than 90% TFE at short contact
times, low conversions, and subatmospheric pressure in the temperature range of 590C900C. Similar results, comparable to subatmospheric pyrolysis,
can be achieved if superheated steam is present
during the pyrolysis. Tetrafluoroethylene yields approaching 95% can be achieved at 80% chlorodifluoromethane conversion if the molar ratio of
steam to CHClF2 is in the range of 7:1 to 10:1.
The products of pyrolysis are cooled, scrubbed
with a dilute basic solution to remove HCl, and dried.
The resulting gas is compressed and distilled to recover the unreacted CHClF2 and to recover high
purity TFE.[10] Tetrafluoroethylene can polymerize

3 FLUOROELASTOMER MONOMERS
violently if it is not inhibited. Because of its high heat
of polymerization, polymer particles may reach temperatures high enough to provide ignition sources for
TFE deflagration. Effective TFE polymerization inhibitors include a variety of terpenes, such as pinene, Terpene B, and d-limonene.[33] Terpenes
were originally thought to act as scavengers of oxygen, a polymerization initiator. However, trace
amounts of oxygen can exist in TFE with terpenes
present. It appears more likely that terpenes undergo
transfer reactions with growing polytetrafluoroethylene free radicals, to form resonance-stabilized radicals that do not undergo further propagation.
Tetrafluoroethylene is highly flammable and can
undergo explosive deflagration in the absence of air:
C2F4 C + CF4
Heat of reaction values of 5762 kcal/mole (at
25C and 1 atm) have been reported for TFE deflagration.[34] Similar amounts of heat are released by
the explosion of black gunpowder.[10] To eliminate
transportation concerns, TFE preparation and polymerization are usually carried out at the same site.

3.4

Hexafluoropropylene (HFP)

Hexafluoropropylene is incorporated at 15 to 25
mole % in copolymers with VDF and TFE to interrupt monomer sequences that would otherwise crystallize. Thus, although HFP tends to raise the glass
transition temperature significantly, this monomer
allows the formation of amorphous elastomers.

3.4.1

HFP Properties

Table 3.5 lists the properties of hexafluoropropylene. It is a colorless, odorless, tasteless, and relatively low toxicity gas, which boils at 29.4C and
freezes at 156.2C. In a four-hour exposure, a concentration of 3,000 ppm corresponded to LC50 in
rats.[35] Critical temperature and pressure of hexafluoropropylene are 85C and 3.254 MPa. Unlike
tetrafluoroethylene, HFP is extremely stable with
respect to autopolymerization and may be stored in
liquid state without the addition of telogen.
Hexafluoropropylene is thermally stable up to
400C500C. At about 600C under vacuum, HFP
decomposes and produces octafluoro-2-butene

29
(CF3CF=CFCF3) and octafluoroisobutylene.[18] Under -radiation, it reacts with oxygen and produces
a 1:1 mole ratio of carbonyl fluoride (COF2) and
trifluoroacetyl fluoride (CF3COF).[36] Heat of combustion of hexafluoropropylene is 879 kJ/mole.[34]
Under basic conditions, hydrogen peroxide reacts
with HFP to form hexafluoropropylene epoxide,
which is an intermediate in the preparation of perfluoroalkyl vinyl ethers.[37][38]
Hexafluoropropylene readily reacts with hydrogen, chlorine, bromine, but not iodine, by an addition
reaction similar to other olefins.[11][39][41] Similarly HF,
HCl, and HBR, but not HI, add to HFP. By reacting
hexafluoropropylene with alcohols, mercaptans, and
ammonia, hexafluoro ethers (CF 3CFHCF 2OR),
hexafluoro sulfides (CF3CFHCF 2SR) and tetrafluoropropionitrile (CF3CFHCN) are obtained. DielsAlder adducts have been identified from the reaction of anthracene, butadiene, and cyclopentadiene
with HFP.[42] Cyclic dimers of HFP can be prepared
at 250C400C under autogenous pressure.[16][17]
Linear dimers and trimers of hexafluoropropylene
can be produced catalytically in the presence of alkali metal halides in dimethylacetamide.[13][15]

3.4.2

HFP Synthesis

Hexafluoropropylene (CF3CF=CF2) was first

prepared by Benning, et al.,[48a] by pyrolyzing polytetrafluoroethylene. They identified this compound
as hexafluorocyclopropane, erroneously. The full synthesis and identification of HFP was conducted by
Henne.[48b] A six-step reaction scheme beginning
with the fluorination of 1,2,3-trichloropropane
(ClCH2CHClCH2Cl) led to 1,2-dichlorohexafluoropropane (ClCF2CFClCF3). The latter was dehalogenated with zinc in boiling ethanol to yield hexafluoropropylene.
There are number of ways to prepare HFP.
Excellent hexafluoropropylene yields from the
thermal degradation of heptafluorobutyrate
(CF3CF2CF2COONa) have been reported.[43] Cracking of tetrafluoroethylene in a stainless steel tube at
700C800C under vacuum is an efficient route
for the production of HFP. TFE conversions up to
72% and HFP yields of 82% have been reported.[44][45] Octafluorocyclobutane (TFE dimer),
octafluoroisobutylene, and some polymers are the
major side products of cracking. The presence of a
small amount (3%10%) of chlorodifluoromethane

30

FLUOROELASTOMERS HANDBOOK

Table 3.5 Properties of Hexafluoropropylene[64]

Property

Value

Molecular weight

150.021

Boiling point at 101.3 kPa, C

29.4

Freezing point, C

156.2

Liquid density vs. temperature (C), g/mL

100 < t < 40
40 < t < 8
8 < t < 30

1.202 0.0041t
1.1507 0.0069t 0.000037t2
1.1325 0.0029t 0.00025t2

Vapor pressure at T K, kPa

196.85< T < 273.15

log10PkPa = 6.6938 1139.156/T

85

Critical temperature, C
Critical pressure, MPa

3.254

Critical density, g/mL

0.60

Liquid density, g/mL

60C
20C
0C
20C

1.105
1.332
1.419
1.498
1078.6

Heat of formation for ideal gas at 25C, H, kJ/mole

Heat of combustion, kJ/mole

879

Toxicity, LC50(rat), 4h , ppm

Flammability limits in air at 101.3 kPa, vol%
a

3,000
Nonflammable for all mixtures of air and HFP

Exposure resulting in fatality of 50% of rats in four hours.

stops the formation of polymer.[46] Thermal decomposition of polytetrafluoroethylene under 20 torr vacuum
at 860C yields 58% hexafluoropropylene.[47] HF
reaction with 3-chloro-pentafluoro-1-propene
(CF2=CFCF2Cl) at 200C, catalyzed by activated
carbon, yields HFP.[47] Hexafluoropropylene can be
prepared from the catalytic degradation of fluoroform
(CHF3) at 800C1000C in a platinum-lined nickel
reactor.[10] Another method is copyrolysis of fluoroform and chlorotrifluoroethylene (CF2=CFCl),[33] or
chlorodifluoromethane and 1-chloro-1,2,2,2-tetrafluoroethane (CHClFCF3),[47] giving good yields of
HFP.
More recently, other methods have been reported for the synthesis of hexafluoropropylene. One

technique involves the pyrolysis of a mixture of

tetrafluoroethylene and carbon dioxide at atmospheric pressure at 700C900C.[49] Conversions
of 20%80% and HFP yields of better than 80%
were obtained. The unreacted tetrafluoroethylene
and carbon dioxide were distilled from the product
and recycled. HFP can be synthesized from
hexachloropropylene via a multi-step process beginning with fluorination.[50] Later steps convert the initial products to CF 3 CFCl CF 3 that is dehalogenated to HFP. Other techniques report on the
synthesis of hexafluoropropylene from the mixture
of a variety of linear and cyclic three-carbon hydrocarbons with a partially halogenated three-carbon
acyclic hydrocarbon.[50]

3 FLUOROELASTOMER MONOMERS

3.5 Perfluoro(methyl vinyl

ether) (PMVE)
Perfluoro(methyl vinyl ether) (PMVE),
CF2=CFCF3, is used in VDF/TFE/PMVE elastomers at levels of 17 to 23 mole % to obtain specialty fluoroelastomers with low glass transition temperatures. In perfluoroelastomers, copolymers with
TFE, PMVE is incorporated at 25 to 40 mole %.
About 25 mole % PMVE is incorporated in ethylene/TFE/PMVE elastomers to get amorphous polymers with reasonable low-temperature characteristics. Other perfluoroelastomers are made with higher
molecular weight perfluoro(alkoxyalkyl vinyl ethers).
PMVE can be made in facilities that synthesize similar monomers used in fluoroplastic copolymers with
TFE, perfluoro(ethyl vinyl ether) and perfluoro(propyl
vinyl ether).

3.5.1

PMVE Properties

Properties of PMVE are shown in Table 3.6.

3.5.2

PMVE Synthesis

Perfluoro(alkyl vinyl ether) is synthesized by

DuPont according to the following steps.
1. Hexafluoropropylene is converted to hexafluoropropylene epoxide (HFPO) by reacting HFP with
oxygen under pressure in the presence of an inert
diluent at 50C250C or with an oxidizer such as
hydrogen peroxide in a basic solution:[52][53]

31
(Basic Solution)
CF3CF=CF2 + H2O2 CF2CFCF2 + H2O

Molecular weight
Boiling point at 101.3 kPa, C
Vapor pressure at 25C, kPa

HFPO
2. HFPO is reacted with a perfluorinated acyl fluoride to produce perfluoro-2-alkoxy-propionyl fluoride:
CF2CFCF2 + RfC=O RfCF2OCFC=O
|
|
\ /
\
O
F
CF3 F
Perfluoro-2-alkoxy-propionyl fluoride
3. Perfluoro-2-alkoxy-propionyl fluoride is reacted
with the oxygen-containing salt of an alkali or alkaline earth metal at an elevated temperature that depends on the type of salt. Examples of the salts include sodium carbonate, lithium carbonate, and sodium tetraborate:[54]
RfCF2OCFC=O + Na2CO3

|
\
CF3 F
RfCF2OCF=CF2 + 2 CO2 + 2 NaF
For synthesis of PMVE, carbonyl fluoride,
F2C=O, is reacted with HFPO in Step 2. Carbonyl
fluoride can be made by oxidation of TFE with oxygen; it is also available as a by-product from HFPO
production.
There are also electrochemical processes for the
production of perfluoro-2-alkoxy-propionyl fluoride.[55]
An alternative synthesis of PMVE is carried out
by Ausimont,[56] using different starting materials:
CO + 2F2 CF3OF
CF3OF + ClFC=CClF CF3OCFClCF2Cl
CF3OCFClCF2Cl + Zn CF3OCF=CF2

Table 3.6 Properties of Perfluoro(methyl vinyl ether)[51]

Property

Value
166
21.8
590

Critical temperature, C

96.15

Critical pressure, MPa

3.41

Toxicity, average lethal concentration (ALC), ppm

10,000

Flammability limits in air, vol.%

7.5 50

32

FLUOROELASTOMERS HANDBOOK

3.6 Olefins: Ethylene and

Propylene
Olefin monomers ethylene and propylene are
used in base-resistant fluoroelastomers. Ethylene is
polymerized with TFE and PMVE at a level of 20
35 mole % to make a base-resistant fluoroelastomer
with good low-temperature characteristics. Propylene is incorporated at 3050 mole % in TFE/P copolymers or TFE/P/VDF terpolymers. Both olefins
exhibit a strong alternating tendency in polymerization with perfluorinated monomers. Conversion of
olefin monomers is usually very high, but they tend
to slow down polymerization since radicals ending
in olefin units are relatively unreactive toward propagation. Ethylene and propylene are readily available
from petrochemical suppliers. High purity is necessary, especially for semibatch polymerization, since
minor impurities such as ethane or propane undergo
transfer reactions that may reduce polymer molecular
weight significantly. Properties of ethylene and propylene are listed in Table 3.7.
Flammability is a major consideration in the handling of ethylene and propylene. However, gaseous
mixtures with TFE have high explosive potential. If
an equimolar mixture of TFE and propylene is ignited at an initial pressure above about 2 MPa, the
rate of pressure rise may be so high that relief devices are ineffective.

3.7 Cure-site Monomers

The major family of VDF/HFP and VDF/HFP/
TFE fluoroelastomers can be cured readily with
bisphenols without incorporation of special cure sites.

In these polymers, specific monomer sequences

present in small amounts provide active sites for cross
linking. Other cure systems, such as peroxide-initiated free radical systems, require incorporation of
more reactive sites. Cure sites must be incorporated
in many specialty fluoroelastomers with main chain
compositions resistant to chemical attack. For good
cross link density, it is generally desirable to incorporate regularly spaced cure-site monomers at about
1 mole % of total monomer units. This allows formation of cross links at intervals of about 100 monomer units. Since most fluoroelastomers have an average degree of polymerization of some 500 to 2000
monomer units, each chain is tied into a network at
multiple points.

3.7.1

Types of Cure-site Monomers

Vinyl monomers containing bromine or iodine

moieties are often used in peroxide-curable fluoroelastomers. Recently, certain fluorinated vinyl
monomers have been incorporated in specialty fluoroelastomers to allow bisphenol curing. Fluorinated
vinyl ethers with functional groups in side chains are
used in perfluoroelastomers to get highly stable cross
links. Many of these monomers require specialized synthesis methods that will not be described here.

3.7.2

Halogenated Vinyl Monomers

Free radical curing of fluoroelastomers is usually effected through reactive bromine- or iodinecontaining sites incorporated at regular intervals along
polymer chains or at chain ends. Apotheker and
Krusic[58] list a number of bromine-containing olefins for use in several families of peroxide-curable

Table 3.7 Properties of Ethylene and Propylene[57]

Property

Monomer
Ethylene

Propylene

Molecular weight

28.05

42.08

Freezing point, C

-169

-185

Boiling point at 101.3 kPa, C

-104

-47

Liquid density at boiling point, g/mL

0.57

0.61

Critical temperature, C

9.6

91.4

Critical pressure, MPa

5.14

4.60

3 FLUOROELASTOMER MONOMERS
fluoroelastomers. Their patent examples include the
cure-site monomers: BTFB, 4-bromo-3,3,4,4-tetrafluorobutene-1, CH2=CH CF2 CF2Br; BTFE,
bromotrifluoroethylene, CF2=CFBr; 1-bromo-2,2difluoroethylene, CF 2 =CHBr; vinyl bromide,
CH2=CHBr; perfluoroallyl bromide, CF2=CF
CF2Br; 3,3-difluoroallyl bromide, CH2=CHCF2Br;
and 4-bromo-perfluorobutene-1, CF2=CFCF2
CF2Br.
Of these monomers, BTFB appears most often
in other DuPont patent examples. BTFB is incorporated at very high conversion, and the transfer activity of the incorporated bromine can be controlled
by adjustment of polymerization conditions to avoid
excessive branching. Most of the other monomers
tend to be incorporated at lower conversion, or
have more reactive bromine moieties that tend to
give excessive branching and gel formation during
polymerization.
The corresponding iodine-containing monomers
(e.g., ITFB) are not as useful, because the more
reactive iodine moieties generally give too much
branching under most polymerization conditions. Instead, iodine has usually been incorporated on chain
ends by the use of iodine-containing transfer agents.
Certain partially fluorinated vinyl monomers
have been found useful to facilitate bisphenol curing
of specialty fluoroelastomers. VDF/PMVE/TFE
elastomers containing 2-HPFP, CF2=CHCF3, can
be cured with carefully formulated bisphenol systems. [59] TFE/P elastomers containing 3,3,3trifluoropropene-1, CH2=CH CF3, also can be
cured with bisphenol.[60]

3.7.3

Functional Vinyl Ethers

Various functional groups have been incorporated in vinyl ethers or fluorinated vinyl ethers for
use as cure-site monomers. Iodine- and brominecontaining fluorinated vinyl ethers have been studied, but have found little use in commercial fluoroelastomer products. Functional perfluoro(alkoxy alkyl
vinyl ethers) [FVEs] are used in TFE/PMVE
perfluoroelastomers developed by DuPont to obtain
vulcanizates with exceptional thermal stability. D.
B. Pattison[61] claimed perfluoroelastomers containing perfluoro(2-phenoxy propyl vinyl ether), curable
with the potassium salt of Bisphenol AF, accelerated with the crown ether dicyclohexyl-18-crown6.[62] FVEs containing cyano moieties have been

33
found to be more versatile cure sites for perfluoroelastomers. A. F. Breazeale [63] claimed
perfluoroelastomers containing perfluoro(8-cyano-5methyl-3,6-dioxa-1-octene) for curing with
tetraphenyltin as adjuvant. A number of other cyano FVEs have been found useful, and several other
cure systems have been developed for perfluoroelastomers containing cyano groups.

3.8 Safety Aspects of

Monomer Handling
Safety issues encountered in the handling of
monomers used in fluoroelastomers fall mainly into
the categories of toxicity, flammability, and
explosivity. Some of these issues have been noted in
the preceding sections on individual monomers. TFE
handling has received much attention from producers, with development of special design considerations and handling procedures.[10] Considerable testing has been done to determine explosion potential
of TFE and mixtures containing TFE under a range
of conditions. Manufacturing processes for various
fluoroelastomers give different potential hazards in
monomer handling. Many monomer mixture compositions are used over wide ranges of temperature
and pressure. Individual monomers are often shipped
and stored in liquid form, then vaporized and mixed
with other monomers for feeding to polymerization
reactors at elevated pressure. Some practical comments on safe handling of monomers are offered
below, but detailed analysis by experts is often necessary to determine proper design and procedures
for particular process situations.

3.8.1

Toxicity Considerations

In most cases, the major fluoromonomers used

in fluoroelastomers are not highly toxic, as noted in
the description of properties in preceding sections.
However, minor impurities present in some fluoromonomers may be highly toxic (e.g., perfluoroisobutylene in HFP). This necessitates setting low exposure limits for operating personnel. Monitoring of
workspaces may be used to detect low levels of fluorinated monomers.
Cure-site monomers containing reactive groups
vary considerably in toxicity. Iodine- and bromine-

34

FLUOROELASTOMERS HANDBOOK

containing fluorocarbons should generally be handled

by procedures designed to avoid personnel exposure.
Sometimes minor differences in molecular structure
can lead to large differences in toxicity. Some of
these materials are produced in small quantities, and
toxicity testing may not be as extensive as that for
major monomers. Thus cautious handling procedures
should be used.

3.8.2

Flammability

Olefin monomers (ethylene and propylene) are

highly flammable. TFE and VDF mixtures with air
are flammable over considerable ranges. However,
other system design considerations often minimize
fire hazards. The necessary design and practices to
avoid explosion and operator exposure, and to assure monomer polymerizability usually lead to reduced flammability hazards.

3.8.3

Explosivity

Most mixtures of major monomers with compositions approximating those of commercial fluoroelastomers are subject to deflagration if an ignition source
is present under conditions prevailing in parts of the
polymerization processes. Producers carry out explosion testing to determine how to avoid deflagrations and how to mitigate the consequences of deflagrations to protect personnel and equipment. A
number of defenses against explosion are employed:
Eliminating potential ignition sources
Limiting monomer compositions, pressure,
and temperature
Minimizing volumes of hazardous monomer
mixtures under pressure
Avoiding formation of more explosive mixtures by partial condensation of mixtures
Minimizing volumes and dead spaces in piping systems
Providing relief devices capable of limiting
pressure rises after deflagration
Putting barricades around process equipment containing particularly hazardous
monomer mixtures

In process areas and equipment containing explosive or flammable monomer mixtures, potential
ignition sources should be eliminated. These include
electrical, mechanical, and concentrated heat
sources. Equipment should conform to electrical classifications appropriate for the monomers handled.
This may include choosing instruments so that the
energy in circuits is below that required for ignition
of particular monomer mixtures. Equipment such as
pumps, compressors, and agitators should be designed to avoid metal-to-metal contact of moving
parts. Surface temperatures should be kept below
autoignition temperatures of monomers. Polymerization initiators should be excluded from monomer
feed systems to avoid premature polymerization in
particles and formation of hot spots. Exclusion of air
from monomer handling systems is necessary, since
trace amounts of oxygen react with TFE and VDF
to form peroxides which may decompose and initiate propagation. Minor leaks in monomer handling
equipment are potential sources of entry for oxygen. Premature polymerization in monomer feed
systems may be suppressed by addition of small
amounts of inhibitors such as terpenes.
For many monomer mixtures used in major fluoroelastomers (e.g., VDF/HFP/TFE and VDF/
PMVE/TFE), it is possible to limit ranges of composition, pressure, and temperature in monomer handling systems to avoid deflagration entirely, or to provide relief systems adequate to avoid equipment
damage or personnel injury if a deflagration occurs.
Such designs may also involve limiting the volume
of monomer mixtures under pressure, so that adequate relief area can be provided. For TFE-rich
mixtures used for several specialty fluoroelastomers,
it may be necessary to limit operating pressures to
avoid ranges in which rates of pressure rise after
onset of deflagration are too high for relief to react
effectively. Barricaded facilities are often necessary
to protect personnel from the potential hazards of
such mixtures.
Process safety is discussed in more detail in
Ch. 4, Production of Fluoroelastomers, covering
various fluoroelastomer families made by different
processes.

3 FLUOROELASTOMER MONOMERS

35

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