5 Cure Systems for Fluoroelastomers �

5.1 � Introduction dehydrofluorination of reactive HFP-VDF sequences

to form double bonds in the polymer chains, followed
Elastomer cure systems are designed to give by reaction of nucleophilic diamine or bisphenol to
stable networks for good mechanical properties and form crosslinks. For VDF/HFP/TFE elastomers with
environmental resistance comparable to that of the high fluorine content, peroxide or radical cure sys-
base polymers. In addition, cure kinetics must be tems have been developed utilizing bromine or io-
controlled to get adequate processing safety (i.e., dine cure sites.
negligible crosslinking at temperatures of 100°C to
140°C). This allows for mixing of compounds on two-
roll mills or in internal mixers, and for extrusion of 5.2.1 Diamine Cure
rod or sheet preforms. At molding temperatures of The first practical cure system for VDF/HFP
160°C to 200°C, an adequate delay is necessary for fluoroelastomers was based on diamine derivatives
mold flow before onset of rapid crosslinking to a with magnesium oxide. The diamine served as both
high state of cure. Compounds should be designed dehydrofluorinating agent and crosslinker, and the
to facilitate good mixing, smooth extrusion, and clean magnesium oxide took up the HF formed. Diamines
demolding of cured parts. such as hexamethylene diamine are too reactive at
These cure system characteristics are also de- low temperature, so derivatives were devised to
sirable for fluoroelastomers, but the nature of the moderate the activity and allow acceptable process-
polymers makes it difficult to attain all the desirable ing safety. The most widely used derivative was the
features noted above. Fluoroelastomers are designed carbamate salt of hexamethylene diamine, +H3N–
for outstanding resistance to high temperature and (CH2)6–NH–COO–, sold by DuPont as Diak No. 1
aggressive fluids, so development of crosslinking curative. A dicinnamylidene derivative (Diak No. 3)
systems with comparable environmental stability is has also been used, ΦCH=CH–CH=N–(CH2 )6 –
a major challenge. In a fluorinated matrix, most cure N=CH–CH=CHΦ, where Φ represents a phenyl
system components have limited solubility and reac- group. The usual acid acceptor in the compound was
tivities are often quite different from those in hydro- MgO with relatively large particle size. Compounds
carbon elastomers. Polymer and cure system de- were relatively simple, containing polymer, diamine,
velopment for the various fluoroelastomer composi- MgO, inert filler, and an optional processing aid. A
tions should be carried out together to obtain com- typical dipolymer formulation is listed below:
pounds suitable for economical commercial produc-
tion of parts. In most cases, the cure system used VDF/HFP Dipolymer 100
initially for each polymer family has been replaced MT black (N990) 30
or modified substantially to attain better processing MgO (Maglite Y) 15
and curing behavior and enhanced final product prop-
Diak No. 1 1.5
erties. This chapter discusses the major cure sys-
tems developed for four fluoroelastomer families: Processing Aid 1
VDF/HFP/(TFE), VDF/PMVE/TFE, perfluoro- MT black is often used as a non-reinforcing filler in
elastomers, and TFE/olefin elastomers. fluoroelastomers. This carbon black is produced by
a thermal process, and has relatively large particles
with few reactive groups on surfaces. A typical pro-
5.2 � VDF/HFP/(TFE) cessing aid is a wax such as carnauba wax that is
somewhat incompatible with the fluoroelastomer at
Copolymers: Diamine, elevated temperature so that it migrates to interfaces
Bisphenol, Peroxide and acts as a flow lubricant or mold release aid.
The mechanism proposed for the diamine cure[1]
Three major systems have been used commer- involves reaction of the amine base with polymer
cially for curing of VDF/HFP dipolymers and VDF/ chains to eliminate HF and form double bonds, fol-
HFP/TFE terpolymers. Two systems are based on lowed by reaction of the nucleophilic diamine with
78 FLUOROELASTOMERS HANDBOOK

the double bonds to form crosslinks with imine struc- accelerator such as benzyltriphenylphosphonium
ture. The exact nature of active sites in the chains chloride,[3] Φ3P+CH2ΦCl– (BTPPC), is necessary,
or of the resulting crosslinks was not determined. along with inorganic bases, usually calcium hydrox-
Water formed from the neutralization of HF by MgO ide and magnesium oxide with small particle sizes.
had to be removed by postcuring in an air oven. With A number of other quaternary phosphonium or am-
water present in vulcanizates at high temperature, monium salts may also be used as accelerators. A
hydrolysis of crosslinks could occur, forming carbo- typical VDF/HFP dipolymer compound used for o-
nyl structures on the polymer chains with regenera- ring seals is as follows:
tion of the amine crosslinking agent. VDF/HFP Dipolymer 100
Except for some use of Diak No. 3 in latex com-
MT black 30
pounding, the diamine cure system is little used now.
The system has considerable processing deficien- MgO (Maglite D) 3
cies, giving premature crosslinking (scorch) at 100°C Ca(OH)2 6
to 140°C and relatively slow cures at molding tem- Bisphenol AF 2
peratures (160°C to 180°C). Vulcanizate properties
are good, but high-temperature compression set re- BTPPC 0.55
sistance is mediocre, and retention of physical prop- The dipolymer has to be designed to have low
erties on long exposure to temperatures above 200°C ionic end groups[4] to avoid interference with the
is relatively poor. accelerator, and polymer molecular weight distribu-
The chemistry of the diamine cure gives some tion may be adjusted to get the desired rheology for
insight into the problem of embrittlement of seals processing.[5] The cure response of this compound
made of VDF/HFP/TFE fluoroelastomers in long- is shown in Fig. 5.1,[6] as measured by oscillating disk
term exposure at high temperatures to automotive rheometry (ODR). The torque sensed by the oscil-
lubricants. Engine oils and transmission lubricants lating disk is a measure of the modulus of the com-
contain large amounts of metal corrosion inhibitors pound at the curing temperature of 177°C. For this
and dispersants that break down to form multifunc- system, no cure occurs for more than 30 minutes at
tional amines. These can react to form enough a processing temperature of 121°C, and a delay of
additional crosslinks to lead to excessive hardness some 2.5 minutes, sufficient to allow mold flow, is
and eventual seal failure. However, actual perfor- observed at the cure temperature of 177°C. Rapid
mance of VDF/HFP/TFE elastomers in automotive crosslinking then occurs, so that a high cure state is
oil seals has been excellent, with rare failures under reached within about 5 minutes. Bisphenol and ac-
extreme service conditions. The high fluorine con- celerator levels can be adjusted to vary cure rates
tent of the terpolymers greatly reduces swelling and states for various applications and processing
by oil and incursion of amines, thus minimizing addi- methods, while retaining the general shape of the
tional crosslinking and giving long service lifetime of cure curve. Crosslink density is proportional to
the seals. Bisphenol AF level in the range 0.5 to 4 phr (parts
per hundred parts of polymer).[7]
Curing and properties are shown in Table 5.1
����� �������������� for a VDF/HFP copolymer product[8] offered for
compression or injection molding of o-rings, extruded
Starting in 1970, the bisphenol cure system displaced
shapes, and calendared sheet. This material is typi-
the diamine system for curing VDF/HFP and VDF/
cal of available commercial products, mostly
HFP/TFE fluoroelastomers. This system has the
precompounds containing bisphenol and accelera-
advantages of excellent processing safety, fast cures
tor, offered by the major fluoroelastomer suppliers.
to high states, excellent final properties, and espe-
The polymer has viscosity, molecular weight distri-
cially high-temperature compression set resistance
bution, and end groups adjusted for excellent rheol-
in seals. While a number of aromatic dihydroxy com-
ogy in mold flow and extrusion with low die swell.
pounds can be used as crosslinking agents, including
The polymer is precompounded with curatives to
the simplest bisphenol (hydroquinone), the preferred
assure the good dispersion necessary for reproduc-
crosslinker is Bisphenol AF, 2,2-bis-(4-hydroxyphenyl)-
ible cure response. Curative levels are not disclosed,
hexafluoropropane, HOΦ–C(CF3)2–ΦOH.[2] An
5 CURE SYSTEMS FOR FLUOROELASTOMERS 79

but the precompound probably contains about 2 phr (DMAC) solution. Schmiegel[10] interpreted these
Bisphenol AF crosslinker and 0.5 phr BTPP+ accel- changes as involving the highly selective
erator (as a salt with the bisphenol, no chloride present) dehydrofluorination of isolated VDF units, in the
to get the high state of cure and moderately high cure chain sequence -HFP-VDF-HFP-, with eventual
rate required for this application. The precompound, formation of a diene structure, as shown in Fig.
VITON® A-401C, has medium viscosity, ML-10 5.3. The concentration of isolated VDF units can
(121°C) = 42. The compound shown meets major be estimated using the monomer sequencing rela-
specifications for fluoroelastomer o-rings, including tionships in Sec. 4.5.3. For a VDF/HFP dipoly-
original stress-strain properties, retention of proper- mer containing 60 wt% VDF, the mole ratio VDF/
ties after aging at 275°C, low swell in fuel and lubri- HFP is Y = 3.52 and the probability of VDF addi-
cating fluid, and resistance to compression set at 200°C. tion to a VDF radical end is P11 = (Y – 1)/Y =
The heat aging data are consistent with very long 0.716. From Eq. (4.58), the fraction Q1 of VDF
service life of bisphenol-cured fluoroelastomers, >3,000 sequences two or more units in length (a = 2) is
hours at 232°C (450°F) and >1000 hours at 260°C 2P11 – P112 = 0.92, so the fraction of VDF in iso-
(500°F). The modest decrease in tensile strength and lated units is 1 – Q1 = 0.08, equivalent to about
increase in elongation at break indicate some network 0.75 moles VDF in -HFP-VDF-HFP- sequences
breakdown at 275°C. per kg polymer. In the reaction scheme shown in
The mechanism of bisphenol curing has been elu- Fig. 5.3, attack by hydroxide results in a double
cidated by W. W. Schmiegel in a series of studies of bond formed by abstraction of the tertiary fluorine
the reactions of various VDF copolymers with a hy- of HFP and the adjacent acidic hydrogen of VDF.
droxylic base, amines, and phenols in a solution, using Fluoride ion initiates rearrangement of the double
19F nuclear magnetic resonance (NMR) measurements bond, and the resulting allylic hydrogen is ab-
to determine structural changes in the polymers.[9][10] stracted by fluoride, a relatively strong base in the
Figure 5.2[10] shows NMR spectra of a VDF/HFP dipolar aprotic DMAC solvent. The reaction se-
copolymer before and after treatment with a hydroxylic quence results in formation of bifluoride and a con-
base in dimethylacetamide, CH3–C(:O)–N–(CH3)2, jugated diene structure in the chain.

Figure 5.1 ODR – Bisphenol cure.[6] Cure response by oscillating disk rheometry (ODR) at 177°C of a compound
optimized for use in o-rings. The maximum cure rate is the initial slope of the curve: ts2, the time to initiation
(increase of the torque by two points from the minimum); tc90 is the time for 90% completion of the cure; and ML,
the degree of the state of the cure. The recipe consists of 100 parts polymer, 30 parts MT Black, 6 parts calcium
hydroxide, 3 parts magnesium oxide, 0.55 parts of benzyltriphenylphosphonium chloride (BTPPC), and 2 parts
of Bisphenol AF.
80 FLUOROELASTOMERS HANDBOOK

Table 5.1 Performance of Bisphenol-Cured VDF/HFP Dipolymer[8]

Compound, phr
VITON® A-401C precompound 100
Magnesium oxide (Maglite D) 3
Calcium hydroxide 6
MT Black (N990) 0
Cure, ODR at 177ºC, Microdie, 3º arc
ML, in-lb 15
MH, in-lb 122
ts2, minutes 1.7
tc90, minutes 3.2
Vulcanizate Properties, Stress/Strain at 23ºC
Press cured 10 minutes at 177ºC
M100, MPa 4.6
TB, MPa 9.9
EB, % 57
Hardness, Durometer A 74
After heat aging 70 hours in air at:
Post cured 24 hours at 232ºC Original
200ºC 232ºC 275ºC
M100, MPa 6.4 6.9 7.2
TB, MPa 13.4 14.0 14.0 10.3
EB, % 199 198 177 240
Hardness, Durometer A 75 78 80 75
Compression set, %, Method B, 25×3.5-mm o-rings
70 hours at 200ºC 15
336 hours at 200ºC 29
70 hours at 232ºC 37
5 CURE SYSTEMS FOR FLUOROELASTOMERS 81

Figure 5.2 NMR of dipolymer before and after base treatment.[10] NMR spectra (94.1 MHz 19F) of VF2 /HFP
polymer before (top) and after (bottom) treatment with hydroxylic base in DMAC solution at 20°C (2,5-
dichlorobenzotrifluoride internal standard). Arrows indicate changes in peak intensities.

Figure 5.3 Reaction of dipolymer and base.[10]

82 FLUOROELASTOMERS HANDBOOK

Schmiegel made further NMR measurements AF crosslinker level of 2 phr corresponds to about
on VDF/HFP dipolymer treated with a cyclic amidine 60 mmol/kg polymer and the BTPPC accelerator
base and Bisphenol AF or its monofunctional analog level of 0.55 phr is considerably lower at about 14
to demonstrate the formation of the diene sequence mmol/kg polymer. Thus, a number of accelerator
shown in Fig. 5.3, and subsequent nucleophilic sub- reaction cycles are necessary to utilize the bisphe-
stitution of the phenol. NMR measurements were nol functionality. This level of bisphenol gives about
also made on a solvent-swollen pseudovulcanizate 120 mmol linkages per kg polymer, corresponding to
of a low molecular weight fluid dipolymer com- an average segment molecular weight between links
pounded with Bisphenol AF, BTPPC, MgO, and of about 8300 Daltons, or 100 mer units. For low to
Ca(OH)2. From these studies, Schmiegel concluded medium viscosity polymers with number average
that, in practical curing situations, a bisphenol-de- molecular weights in the range 80,000 to 100,000
rived phenolate attacks the diene structure in the Daltons, this relatively high crosslink density corre-
polymer, leading to dienic phenyl ether crosslinks, as sponds to about 10 to 12 links per chain.
shown in Fig. 5.4. When a phosphonium salt such as It should be noted that the total concentration of
BTPPC is used as accelerator, the phosphonium ion reactive -HFP-VDF-HFP- sequences in commer-
is believed to undergo several cycles of conversion cial dipolymer is far higher than that needed for cur-
from fluoride (or bifluoride), to hydroxide, to phe- ing. Schmiegel[10] found that, in the absence of free
noxide, to fluoride, before exhaustion of the phenol. bisphenol, hydroxide attack on the diene structure
Ultimately, the benzyltriphenylphosphonium ion is could form a dienone, as shown in Fig. 5.5. This
converted to triphenylphosphine oxide, which is prob- structure would be susceptible to further hydrolysis
ably removed during the oven post cure. For the o- and chain cleavage. Commercial bisphenol
ring compound described previously, the Bisphenol vulcanizates contain excess calcium hydroxide, so
exposure to hot water or steam can lead to
eventual network breakdown.
VDF/HFP/TFE fluoroelastomers with
high fluorine content and greater fluid resis-
tance than the VDF/HFP copolymers dis-
cussed above generally give slower cures.
Schmiegel[10] studied reactivities in solution of
such terpolymers and of several VDF/TFE
thermoplastic compositions made by the au-
thor. He found that all sequences of single
VDF units isolated between perfluorinated
monomer units could be dehydrofluorinated
readily, but ease of nucleophilic attack on the
resulting unsaturated structures varied consid-
erably. Unsaturated structures from sequences
-TFE-VDF-TFE- and -TFE-VDF-HFP-
had low reactivity toward nucleophiles, and
thus, gave little crosslinking by bisphenols.
Diene structures from -HFP-VDF-HFP- and
-HFP-VDF-TFE- were readily attacked by
nucleophiles and crosslinked by bisphenols.
Rates of gelation by Bisphenol AF and a cy-
clic amidine base in DMAC solution were
higher for VDF/HFP/TFE (61/17/22 mole %)
terpolymer than for VDF/HFP (78/22 mole %)
dipolymer. Thus, the slower terpolymer cures
in practical bulk systems appear to be caused
by the more highly fluorinated medium. The
Figure 5.4 Bisphenol crosslinking scheme.[10]
5 CURE SYSTEMS FOR FLUOROELASTOMERS 83

with accelerators containing chloride, bromide, or

iodide anions. In addition to hydrogen sulfate, other
anions associated with tetrabutylammonium ion give
little or no mold fouling, including fluoride, dihydrogen
phosphate, acetate, methane sulfonate, toluene sul-
fonate, periodate, and bisphenolate. TBAHS was also
shown in patent examples to work well with
bisphenols other than Bisphenol AF. TBAHS and
BTPPC are compared in terpolymer compounds in
patent examples from Ref. 13, summarized in Table
5.2. The terpolymers have composition VDF/HFP/
TFE = 45/30/25 wt % (68.5% F) and 35/35/30 wt %
(70% F), and were compounded with 30 phr MT
black, 4.5 phr calcium hydroxide, and 3 phr high ac-
tivity magnesium oxide, and curatives as listed in
Table 5.2. Compared to BTPPC in these high-fluo-
Figure 5.5 Hydroxide attack on diene.[10] rine terpolymers, TBAHS gives lower compound
viscosity, faster cures to higher states, better com-
terpolymer is less polar, so it is less able to support pression set resistance, and much less fouling in com-
the ionic intermediates formed during curing. Also pression molding tests carried out for fifty molding
the solubility and mobility of curatives are lower in cycles.
high-fluorine terpolymers.
A number of accelerators have been developed 5.2.3 Peroxide Cure
for bisphenol curing as alternatives to phosphonium
salts such as BTPPC. Patent cross-licensing be- Fluoroelastomers cured with peroxides, or free
tween DuPont and 3M initially excluded Daikin and radicals, exhibit improved resistance to steam, hot
Montedison from using the preferred phosphonium water, and aqueous acids over those cured with
accelerators. Daikin developed various bases con- bisphenols. Peroxide-cured compounds generally do
taining nitrogen heterocyclic structures, including not contain much unsaturation and inorganic bases,
cyclic amidines such as 8-benzyl-1,8-diaza- so they are less susceptible to attack by aqueous
bicyclo[5,4,0]-7-undecenium chloride. Montedison fluids. On the other hand, the crosslinking agents
developed accelerators based on amino phosphinic (“radical traps”) used give lower thermal stability
derivatives[11] and bis(triarylphosphin)iminium than bisphenols. For peroxide curing, fluoroelas-
salts.[12] Most of these accelerators were included tomers must contain sites reactive toward free radi-
with bisphenol as ingredients in proprietary fluo- cals, usually bromine or iodine introduced within
roelastomer precompounds offered commercially; chains by incorporation of cure-site monomers or at
exact compositions are generally not disclosed by chain ends by chain-transfer agents. In the late 1970s,
suppliers. As noted for the DuPont compound de- DuPont offered the first commercial peroxide-cur-
scribed in Table 5.1, a useful variant of a phospho- able fluoroelastomers, containing about 0.5%–0.9%
nium accelerator is its bisphenolate salt, thus elimi- bromine in cure-site monomers such as 4-bromo-
nating the halide anion that could cause demolding 3,3,4,4-tetrafluorobutene (BTFB).[14] Conditions in
problems. the continuous emulsion polymerization process used
Quaternary ammonium salts are also effective can be adjusted to minimize unwanted transfer to
accelerators for bisphenol cures. In particular, incorporated bromine-containing units, thus avoiding
Schmiegel and Carlson[13] found that tetrabutyl- excessive long-chain branching. Such transfer and
ammonium hydrogen sulfate (TBAHS) gives fast branching reactions are more difficult to minimize in
cures of high-fluorine VDF/HFP/TFE terpolymers semibatch processes, since all the polymer formed
to high states with good scorch resistance. A major remains in the reactor exposed to free radical activ-
advantage is that compounds with TBAHS accel- ity until the end of the batch polymerization. Daikin
erator give much less mold fouling than compounds later developed the semibatch “living radical” iodine
84 FLUOROELASTOMERS HANDBOOK

Table 5.2 Comparison of Accelerators in Bisphenol Cures of VDF/HFP/TFE Terpolymer Compounds[13]

Elastomer Terpolymer, 68.5% F Terpolymer, 70% F

Patent Example 4 3 Comparative 2 5 Comparative 3
Curatives, phr
Bisphenol AF 1.90 1.90 1.9 2.00 2.3
TBAHS 0.67 1.00 0.86
BTPPC 1.00 1.03
Mooney Scorch, 121°C
Minimum torque 54 49 72 48 62
Minutes to 1-point rise 15 >30 >30 >30 8
Oscillating disk rhometer, ASTM D-2084, 177°C
MH-ML, N·m 5.3 4.7 4.6 3.9 3.8
ts0.2, minutes 2.9 2.8 2.5 4.5 4.2
tc90, minutes 4.3 3.8 4.2 6.7 8.9
Stress/Strain, 23°C
After press cure (10 min/177°C)
M100, MPa 5.1 4.7 4.0 4.2 4.4
TB, MPa 12.1 11.3 10.2 11.3 10.0
EB, % 225 230 280 280 320
After post cre (24 h/232°C)
M100, MPa 7.0 6.7 6.1 5.4 5.7
TB, MPa 15.2 14.7 13.3 14.4 14.8
EB, % 170 180 187 210 255
After heat aging (70 h/275°C)
M100, MPa 3.7 4.0 3.7 3.0 3.5
TB, MPa 11.2 10.4 10.4 8.9 7.2
EB, % 245 240 280 345 430
Compression Set, ASTM
D-395-61, Method B, %, 23 30 28 38 50
70 h/200ºC
Deposits in mold
None None Heavy None Heavy
after 50 cycles
5 CURE SYSTEMS FOR FLUOROELASTOMERS 85

transfer process to make peroxide-curable polymers cyanurate (TMAIC), and triallyl cyanurate (TAC)
with very narrow molecular weight distribution and are shown in Fig. 5.6. With its hindered allyl groups,
iodine incorporated on most chain ends.[15] Using the alternative trap TMAIC does not
multifunctional radical traps to link chain ends re- homopolymerize like TAIC, thus it gives slower
sults in uniform networks that give low compression cures. TAC gives good cure rates and states, but
set. Thermal resistance of such chain end-linked lower thermal stability than vulcanizates crosslinked
networks is limited, since loss of relatively few link- with TAIC or TMAIC. Small amounts of metal ox-
ages results in formation of many loose long chain ides are useful for absorbing traces of hydrogen fluo-
segments that do not contribute to elastic recovery, ride that may be generated during curing. For curing
so that physical properties deteriorate considerably. a fluoroelastomer containing about 0.7% bromine
More recently, fluoroelastomers have been made incorporated through a cure-site monomer such
with iodine end groups and bromine- or iodine-con- BTFB, a typical recipe might be:
taining cure-site monomers to get higher functional- Fluoroelastomer 100
ity per chain.[16]
MT black (N990) 30
In a study of peroxide curing of bromine-con-
taining fluoroelastomers,[17] DuPont workers ob- ZnO 3
tained satisfactory cures with aliphatic peroxides 2,5- Peroxide (101XL) 3
dimethyl-2,5-di-�-butylperoxyhexane, and 2,5-dim- TAIC 3
ethyl-2,5-di-�-butylperoxyhex-3-yne, available from
Atochem as Luperco 101XL and 130XL (45% ac- This recipe would give time to 90% cure, for
tive ingredient on inert support). These peroxides about 3 minutes at a temperature of 177°C. Ordi-
have a half life of 0.8 and 3.4 minutes at 177°C, narily, an oven post cure, say 24 h/232°C, is used to
respectively. Lower molecular weight aliphatic per- develop optimum properties. The cure state of com-
oxides such as di-�-butylperoxide were found to be pounds based on bromine-containing fluoroelas-
active, but too volatile, being partially lost during com- tomers increases significantly during post curing.
pound mixing. Peroxides with aromatic substituents Fluoroelastomers with iodine cure sites cure faster
(e.g., dicumyl peroxide), gave variable results, prob- to higher cure states during molding, and do not re-
ably because of excessive acid-catalyzed decom- quire long post cures at high temperatures.
position in the fluoroelastomer matrix. Of the radi- In the DuPont peroxide curing study[17] cited,
cal traps tested, the most effective crosslinker is cure rate and state as measured by ODR modulus
triallylisocyanurate (TAIC), as judged by cure state increase were directly proportional to the level of
and compression set of vulcanizates. Other effec- bromine-containing cure-site monomer in the poly-
tive crosslinkers contain unhindered allyl or vinyl mer. Compression set of vulcanizates improved with
groups attached to N, O, or Si; all are electron-rich cure-site content, with the effect leveling off above
groups. Electron-poor traps effective in hydrocar- about 20 mmol cure-site/kg polymer. At constant
bon elastomers, such as �-phenylene-bis-maleimide, cure-site monomer concentration, cure rate in-
are ineffective in fluoroelastomers. Structures of the creases with increasing levels of both peroxide and
effective radical traps TAIC, trimethallyl iso- radical trap. Cure rate also increases strongly with

N
N CH2 CR CH 2 CH 2 CH CH 2 O C C O CH2 CH CH 2
O C C O

N N

CH2 CR CH 2 N N CH2 CR CH 2 C

C O CH2 CH CH 2
O

T AlC R=H
T M AlC R =CH 3 TAC

����������� Radical traps for peroxide curing of fluoroelastomers.

86 FLUOROELASTOMERS HANDBOOK

increasing temperature in the range of 160°C to amounts of methyl bromide and volatile hydrocar-
204°C, with ODR cure times correlated with perox- bons formed from methyl radicals were low relative
ide half life (approximately the same relationship for to the acetone level. This suggests that most of the
peroxides 101XL and 130XL). The state of cure methyl radicals react with the allyl groups of the
depends mostly on the radical trap level. The cure TAIC radical trap to form radical adducts that may
state increases with peroxide 101XL only up to about propagate with other allyl groups, undergo transfer
3 phr. reactions with bromine groups on polymer chains,
Measurements of volatile materials generated or add to polymeric radicals. The TAIC level of 4
during curing at 190°C give further insight into the phr in the compound tested corresponds to about
various reactions occurring in peroxide curing of fluo- 480 mmoles of allyl functionality per kg polymer, far
roelastomers. The polymer used in the study con- in excess of that needed for crosslink formation. The
tained about 56 mmol Br/kg polymer (about 0.45% amount of water evolved amounts to about 0.3% on
Br). The recipe used was: polymer, consistent with levels expected in isolated
Fluoroelastomer 100 polymer and calcium hydroxide.
Consistent with these results, Fig. 5.7 shows the
MT black (N990) 30
probable reactions resulting from initiator decompo-
Calcium hydroxide 4 sition in a typical compound. Most of the primary t-
Peroxide (101XL) 4 butoxy radicals undergo ß-scission to acetone and
TAIC 4 methyl radicals. A major fraction of the methyl radi-
cals add to allyl functionality of the TAIC coagent to
The peroxide level corresponds to about 60 form radical adducts. Only a minor fraction of me-
mmol/kg polymer. The measured levels of volatile thyl radicals are involved in transfer reactions with
products are listed in Table 5.3. No volatiles were fluoroalkyl bromide sites on polymer chains to form
formed from the large 2,5-dimethyl-2,5-oxyhexane methyl bromide and polymeric radicals. If the radi-
radical fragment of the peroxide, but the amount of cal trap concentration is reduced considerably, the
acetone formed was about 80% of the maximum amount of methyl bromide increases by up to a fac-
possible for fragmentation of the primary t-butoxy tor of two, still relatively low versus the total amount
radicals into acetone and methyl radicals. The sum of methyl radicals produced.
of the amounts of t-butanol (formed by hydrogen Proposed crosslinking reactions are shown in Fig.
transfer to t-butoxy radicals) and isobutene (formed 5.8. Coagent adduct radicals react with bromine cure
from dehydration of t-butanol) was about eightfold sites on polymer chains to form polymer radicals.
lower than the amount of acetone evolved. The Allyl groups add to these radicals to form crosslinks.
The idealized structure shown for crosslinks in Fig.
5.8 is not likely for TAIC radical trap at usual levels
Table 5.3 Volatiles Generated in Peroxide Curing[17] >1 phr in compounds. The main reaction for TAIC
is polymerization to form oligomers; attachment to
Amount generated, polymer chains is a side reaction. However, TMAIC
Compound does not homopolymerize, so the structure shown is
mmoles/kg polymer
more likely for this trap.
Acetone 94.5
Stock and vulcanizate properties are shown in
t-Butanol 7.8 Table 5.4 for peroxide curing of VDF/HFP/TFE
Viton® types containing bromine cure sites from in-
Isobutene 3.9
corporated monomer.[18] Viton® GBL-900 and GBL-
Methyl bromide 1.8 200 contain about 68% fluorine; GBL-200 also has
Methane 26.8 iodine end groups. GF contains about 70% fluorine
for enhanced fluid resistance. All compounds con-
Ethane 2.6 tain 100 Polymer, 30 MT black (N990), 3 Zinc ox-
Propane + ide, 1 Carnauba wax, 0.75 VPA#3 processing aid, 2
4.1 TMAIC, and 4 Peroxide (Luperco 101XL). Slabs
propylene
were press cured 10 min/177°C and post cured 24
Water 166 h/232°C.
5 CURE SYSTEMS FOR FLUOROELASTOMERS 87

Figure 5.7 Probable reactions from peroxide Figure 5.8 Proposed crosslinking mechanism.[17]
decomposition.[17]

These bromine-containing polymers have fairly factory for curing these iodine-containing polymers.
good thermal resistance, showing good retention of The hindered methallyl groups add much more slowly
properties after short-term service at 232°C. Based to chain radicals, so that other reactions may occur
on approximate bromine and iodine levels, and num- and limit the efficiency of crosslinking. Good mold
ber average molecular weights, the average chain release is obtained when TAIC is used with iodine-
contains some 4–10 cure sites. Thus, most chains containing polymers. Good properties are obtained
are linked into the network at several points, so deg- with little or no post cure. Only a press cure of 15–
radation of linkages must be extensive to cause sig- 20 minutes at 170°C was used for the compound
nificant loss of mechanical properties. Mold sticking shown in Table 5.5, with the recipe: 100 polymer
and fouling are often encountered in peroxide cur- (Dai-el® G-902), 20 MT black, 3 magnesium oxide
ing of bromine-containing fluoroelastomers. Process- (low activity grade), 3 peroxide (equivalent to
ing and release aids are usually included in their com- 101XL), and 3 TAIC.
pounds to minimize molding problems. Premature curing during processing (scorch) of
Typical peroxide cure properties of a VDF/HFP/ peroxide compounds can be minimized, if necessary,
TFE (70% fluorine) terpolymer with iodine end by addition of small amounts of phenolic or amine
groups are shown in Table 5.5.[19] The polymer is free radical inhibitors such as 2,6-di-t-butyl-4-
Daikin Dai-el® G-902, which contains an average methylphenol.[17] Long-chain aliphatic amines may
of about 1.8 iodine ends per chain. Thus chains are also serve as processing aids.
tied to the network at no more than two points. Gen- A number of peroxide-curable fluoroelastomers
erally, cured products are satisfactory for long-term have been developed recently that have iodine on
service up to 200°C. At higher temperatures, ther- most chain ends and additional iodine in cure-site
mal breakdown of a relatively small fraction of link- monomer units incorporated along chains.[20] Such
ages results in severe loss of mechanical properties. polymers give fast cures to high state, excellent
Since the iodine sites are very reactive toward radi- demolding characteristics, excellent compression set
cals, cures are very fast. Usually TAIC is used for resistance, and thermal resistance comparable to that
crosslinking, since the allyl groups add readily to flu- of bromine-containing polymers such as those in
orinated radicals at chain ends. TMAIC is not satis- Table 5.4.
88 FLUOROELASTOMERS HANDBOOK

Table 5.4 Peroxide Curing of VDF/HFP/TFE Fluoroelastomers Containing Bromine Cure Sites[18]

Polymer: Viton® GBL 900 GBL 200 GF

Stock Properties
Viscosity, ML-10(121ºC) 86 37 87
Mooney Scorch, MS (121ºC)
Minimum, in lb 44 19 46
Time to 2 point rise, minutes >30 >30 >30
ODR at 177ºC, Microdie, 3º arc
ML, in-lb 21 10 18
MH, in-lb 79 77 70
ts2, minutes 2.2 1.6 2.3
tc90, minutes 7.4 6.8 7.4
Vulcanizate Properties
Stress/Strain at 23ºC – Original
M100, Mpa 5.9 4.3 7.0
TB, Mpa 20.0 19.1 20.6
EB, % 220 315 261
Hardness, Durometer A 75 79 80
Stress/Strain at 23ºC – Aged 168 h/200ºC
M100, Mpa 5.7 4.7 7.1
TB, Mpa 21.1 19.2 21.2
EB, % 227 267 228
Hardness, Durometer A 76 78 81
Stress/Strain at 23ºC – Aged 70 h/232ºC
M100, Mpa 8.7 8.8 8.6
TB, Mpa 20.7 15.9 21.1
EB, % 178 146 201
Hardness, Durometer A 76 78 81
Compression Set, Method B, O rings, %
70 h/23ºC 17 18 18
70 h/200ºC 51 68 63
168 h/200ºC 66 81 72
Fluid Resistance, Volume Swell, %
Fuel C, 168 h/23ºC 5 5 3
Methanol, 168 h/23º 65 65 4
Conc. Sulfuric Acid, 168 h/70ºC 4 6 6
ASTM Oil #3, 168 h/150ºC 3 2 2
Water, 168 h/100ºC 9 9 8
Low Temperature Properties
Brittle Point, ºC –46 –46 <54
Glass Transition Temperature, ºC –15 –16 4
5 CURE SYSTEMS FOR FLUOROELASTOMERS ­ 89

Table 5.5 Peroxide Curing of VDF/HFP/TFE Fluoroelastomer Containing Iodine Cure Sites at Chain Ends[19] ­

Polymer: Dai-el® G-902

Stock Properties
Mooney Scorch, ML at 145ºC
Time to 5-point rise, minutes 6.7
JSR Curelastometer, 170ºC
tc90, minutes 1.3
Vulcanizate Properties
Stress/strain – original, press cured
M100, MPa 2.7
TB, MPa 16.9
EB, % 320
Hardness, JIS A 72
Compression set, %
70 h/120ºC 13
265 h/120ºC 16
Stress/strain – after 70 h/40ºC in fuel D
M100, MPa 2.1
TB, MPa 15.1
EB, % 320
Hardness, JIS A 66
Volume swell, % 5.9

5.3 � VDF/PMVE/TFE mers, the most base-sensitive sites are the adjacent
PMVE and VDF units in the sequences -PMVE-
Elastomers: Peroxide
VDF-PMVE- or -PMVE-VDF-TFE. Base attack
(Bisphenol) results mostly in the removal of the elements of
trifluoromethanol, HOCF3, from the chain, rather than
HF. Removal of –OCF3 groups gives unsaturated
When curing of VDF/PMVE/TFE terpolymer structures that are unreactive toward nucleophile
is attempted with standard bisphenol or diamine reci- addition, so that little crosslinking occurs with di-
pes, the result is formation of excessive fissures and amines or bisphenols. Trifluoromethanol is unstable,
porosity in poorly cured molded parts. Base treat- breaking down into HF and carbonyl fluoride, which
ment of these polymers generates a large amount of in turn hydrolyzes to more HF and CO2. Neutraliza-
volatiles, with little crosslinking with nucleophiles. In tion of HF with MgO or Ca(OH)2 generates addi-
his study of crosslinking of VDF copolymers with tional water. The large amounts of HF, CO2, and
nucleophiles, Schmiegel[10] clarified the reactions of H2O volatiles formed in the course of these reac-
bases with VDF/PMVE/TFE polymers in solution, tions leads to excessive porosity in undercured
using 19NMR and specific amines to identify the re- vulcanizates. Typical reactions are outlined below
sulting products. Analogous to HFP-containing poly- (X = F or OCF3):
90 FLUOROELASTOMERS HANDBOOK

is readily dehydrofluorinated to form an unsatur-

ated site,

which is highly reactive toward addition of nucleo-

philes such as bisphenols. Independent of adjacent
monomer units, 2H-PFP sites are more reactive than
In early attempts to attain successful bisphenol sequences of isolated VDF units flanked by
curing of this family of polymers, HFP was substi- perfluoromonomer units. Other components of the
tuted for part of the PMVE. The resulting VDF/ cure recipes are chosen to facilitate crosslinking at
HFP/PMVE/TFE tetrapolymers had to contain more 2H-PFP sites while minimizing reactions involving
HFP than PMVE to get adequate curing. Unfortu- VDF sequences. Preferably, HF generated is ab-
nately, the low-temperature characteristics of such sorbed by molecular sieve zeolites, crystalline alu-
tetrapolymers were little better than those of VDF/ minosilicates, and by metal oxides such as MgO or
HFP/TFE terpolymers with similar VDF content. CaO. Usually, calcium hydroxide is not used, since
In the 1970s, DuPont introduced peroxide-cur- neutralization with HF would generate water, which
able VDF/PMVE/TFE elastomers with bromine- would facilitate attack on VDF sites. While thermal
containing cure-site monomers.[14] Compounding and black filler can be used, curing is enhanced with a
curing are the same as described in the previous modified silane-coated mineral filler, such as
section on peroxide curing of VDF/HFP/TFE fluo- aminosilane-coated wollastonite (calcium metasili-
roelastomers. Analogous VDF/PMVE/TFE fluo- cate, CaSiO3). In a patent example, bisphenol cur-
roelastomers with iodine end groups and bromine- ing of a VDF/PMVE/TFE elastomer (labelled 1B)
or iodine-containing cure-site monomers were de- containing 2H-PFP cure-site monomer is compared
veloped for better processing and curing character- to peroxide curing of a similar commercial fluoroelas-
istics. Peroxide-cured vulcanizates have the desired tomer (control) with cure-site monomer 4-bromo-
improved low-temperature characteristics and good 3,3,4,4,-tetrafluorobutene (BTFB). Polymer charac-
fluid resistance for which this family of fluoroelas- teristics, cure recipes, and properties are shown in
tomers was developed. Peroxide cure characteris- Table 5.7.
tics and vulcanizate properties are shown in Table In other curing examples, a polymer similar to
5.6 for two fluid-resistant (67% fluorine) VDF/ 1B was formulated with 2 phr Bisphenol AF and 45
PMVE/TFE fluoroelastomers, Viton® GFLT with a phr of various epoxysilane- or aminosilane-coated
bromine-containing cure-site monomer incorporated, wollastonite fillers to get much faster cures (90%
and Viton® GFLT-300 with iodine on chain ends in cure times near 2 minutes) to somewhat higher states
addition to bromine cure sites.[21] The compounds with better compression set resistance. No spong-
contain 100 polymer, 30 MT black (N990), 3 zinc ing was observed in these vulcanizates. This devel-
oxide, 2.5 peroxide (Luperco 101XL), and 2.5 TAIC. opment allows application of the bisphenol cure sys-
Slabs were press cured for 8 minutes at 177°C and tem, with its improved processing characteristics and
post cured for 24 hours at 232°C. thermal stability, to be applied to the VDF/PMVE/
Recently, Schmiegel and Bowers[22] developed TFE family of fluoroelastomers.
practical bisphenol cures of VDF/PMVE/TFE Resistance of VDF/PMVE/TFE vulcanizates to
fluoroelastomers with a specific cure-site monomer fluids containing organic amines is better than that
and special compounding. The cure-site monomer, of VDF/HFP/TFE vulcanizates because multifunc-
usually incorporated at levels of 1%–3%, is 2-hydro- tional amines do not readily add to unsaturated sites
pentafluoropropylene (2H-PFP), CF2=CH–CF3. in the PMVE-containing polymers. Thus, they do
The incorporated monomer unit, not fail by excessive crosslinking, therefore, they do
not cause the surface to crack or cause the embrittle-
ment produced in HFP-containing polymers.
5 CURE SYSTEMS FOR FLUOROELASTOMERS ­ 91

Table 5.6 Peroxide Curing of VDF/PMVE/TFE Fluoroelastomers Containing Bromine Cure Sites[21] ­

Polymer: Viton® GFLT GFLT-300

Stock Properties
Mooney Scorch, MS at 121ºC
Minimum, in-lb 47 29
Time to 5-point rise, minutes >30 28
ODR at 177ºC, Microdie, 3º arc
ML, in-lb 24 17
MH, in-lb 89 101
ts2, minutes 1.1 0.9
tc90, minutes 5.2 4.4
Vulcanizate Properties
Stress/strain at 23ºC – original
M100, MPa 7.5 7.0
TB, MPa 18.7 17.9
EB, % 180 180
Hardness, durometer A 72 72
Stress/strain at 23ºC – Aged 70 h/250ºC
M100, MPa 7.2 5.3
TB, MPa 17.9 16.7
EB, % 200 253
Compression set, method B, O-rings, %
70 hours at 200ºC 33 33
Fluid resistance, volume swell, %
Fuel C, 168 hours at 23ºC 5 4
Methanol, 168 hours at 23ºC 8 6
Glass transition temperature, ºC -23 -25
92 FLUOROELASTOMERS HANDBOOK

Table 5.7 Curing of VDF/PMVE/TFE Elastomers with Bisphenol or Peroxide[22]

Polymer Example 1B Control

Composition, wt %
VDF 54.1 55
PMVE 33.9 34.8
TFE 10.0 10
2H-PFP 2.0 --
BTFB -- 1.2
Viscosity
Inherent viscosity (MEK, 30ºC) 1.10 1.3
ML-10 (121ºC) 89 90
Glass transition temperature, ºC -29 -30
Formulation Example 1B Control
Polymer 100 100
MT Black (N990) 30 30
Calcium oxide 6 --
Calcium hydroxide -- 5
Molecular sieve 13X 3 --
Peroxide 101XL -- 4
TMAIC -- 2
TBAHS 0.5 --
Bisphenol AF 2.5 --
Cure Characteristics Example 1B Control
ODR at 180ºC
ML, dN·m 7.1 10.3
MH, dN·m 43.9 56.8
ts2, minutes 3.2 1.8
tc50, minutes 7.3 3.7
tc90, minutes 18.0 7.2
Vulcanizate Properties (press cure 15 minutes at180ºC, post cure 24 hours at 232ºC)
Stress/strain at 23ºC
M100, MPa 5.0 6.1
TB, MPa 15.1 20.1
EB, % 244 212
Hardness (shore A) 71 69
TR-10, ºC -26 -28
Compression set, pellets, %
70 hours at 200ºC 32 26
5 CURE SYSTEMS FOR FLUOROELASTOMERS 93

��� �������������������� perfluoro(2-phenoxypropyl vinyl ether) to allow

bisphenol curing.[27]
�������� �������
Improved performance has been achieved with
DuPont workers developed perfluoroelastomers TFE/PMVE perfluoroelastomers containing the
based on TFE/PMVE copolymers. These polymers cure-site monomer perfluoro(8-cyano-5-methyl-3,6-
are almost as resistant to fluids as polytetrafluoroet- dioxa-1-octene), CF2=CF–O–CF2–CF(CF3)–O–
hylene thermoplastics, and are usable at tempera- CF2–CF2–CN, 8-CNVE.[28] Tetraphenyltin is used
tures up to 315°C (600°F). A major problem in early to catalyze formation of highly stable triazine
product development was to find practical cure sys- crosslinks, schematically shown in Fig. 5.9.[29] The
tems with thermal stability of crosslinks comparable curing reaction does not require a crown ether sol-
to that of the polymer. The system used for the first vent. A reasonable state of cure is obtained in the
commercial products is based on bisphenol curing press, so that parts can be removed from a hot mold
of perfluoroelastomers containing the cure-site mono- without sponging. As with the K2AF system, a long
mer perfluoro(2-phenoxypropyl vinyl ether).[23] The oven post cure at high temperature is necessary to
preferred curing system uses the dipotassium salt of develop full properties. It seems likely that the long
Bisphenol AF (K2AF) with a crown ether such as cure time is necessary to form the triazine crosslink
dicyclohexyl-18-crown-6, which coordinates with structures, each involving three cyano groups on
potassium ion and facilitates transport of ionic spe- polymer chains. Thermal stability of the triazine
cies to cure sites.[24] The crosslink formation reac- vulcanizates is high. Kalrez ® K4000 series
tion presumably involves removal of a fluorine from perfluoroelastomer parts are unchanged from origi-
a pendent perfluorophenoxy group and addition of nal post cured properties after aging 18 days at 288°C
bisphenolate ion at this site to form an ether linkage. in air. They retain useful properties after similar ag-
To avoid excessive degradative transfer during in- ing at 316°C: 100% modulus decreases by <20%,
corporation of the perfluorovinyl ether cure-site tensile decreases by <40%, and elongation at break
monomer units, polymerization temperatures must is unchanged.[26]
be low, typically 65°C to 85°C. Persulfate-sulfite As with VDF-containing fluoroelastomers, bro-
redox initiation systems are used for these polymers, mine-containing monomers may be incorporated in
resulting in mostly sulfonate end groups. Ionic clus- perfluoroelastomers to allow peroxide curing.[14] Io-
ters of these end groups are stable at temperatures dine end groups may be incorporated by transfer to
over 200°C, so polymer viscosity is extremely high get faster cures.[30] Daikin applied its “living radi-
at processing and molding temperatures. Mixing with cal” polymerization technology[15] to obtain perfluoro-
fillers (e.g., 10 phr SRF black) and curatives is diffi- elastomers with narrow molecular weight distribu-
cult, as is fabrication of preforms for molding of parts. tion and mostly iodine end groups. The perfluoro(alkyl
Little cure occurs in a press at 190°C, so the mold vinyl ether) copolymerized with TFE in Daikin
must be cooled before removal of parts to prevent Perfluor® has a relatively long alkyl side chain, prob-
sponging. Curing is completed in a long post cure, ably perfluoro(2-propoxypropyl vinyl ether). Since
some two days at temperatures up to 288°C (550°F) the iodine-containing perfluoroelastomers have ex-
under nitrogen. Because of the great difficulties en- cellent processing characteristics, Daikin elected to
countered in processing and curing, DuPont decided sell the gum elastomer to fabricators. Peroxide-cured
to make and sell perfluoroelastomer fabricated parts
rather than polymer.[25] Compared to parts from
hydrofluoroelastomers, the resulting Kalrez® K1000
series perfluoroelastomer parts have much higher
thermal stability: after 20 days at 288°C in air, 100%
modulus decreases by <25%, tensile strength de-
creases by <15%, and elongation at break increases
by 120%.[26] In a later development, Finlay found
that a small amount of a hydrocarbon-containing
monomer such as VDF could be incorporated in ���������� Crosslinking structure for nitrile perfluoro-
TFE/PMVE polymer in place of the high-cost elastomers.[29]
94 FLUOROELASTOMERS HANDBOOK

perfluoroelastomer vulcanizates are resistant to most life at temperatures up to 315°C. The hydrocarbon
fluids, except oxidizing materials, and have outstand- crosslinks of the peroxide-cured polymer with –RfBr
ing resistance to hot water and steam. Thermal re- cure sites begin to break down significantly at 225°C.
sistance is similar to that of other peroxide-cured The bisphenol-cured polymer is intermediate in heat
fluoroelastomers, adequate for long-term service up resistance. Swell of these perfluoroelastomer vul-
to 200°C. Since the bulk of perfluoroelastomer end canizates is low in most fluids. However, as with
uses require outstanding fluid resistance, but not re- other fluoroelastomers, bisphenol vulcanizates are
sistance to extremely high temperatures, peroxide- susceptible to swell and breakdown in hot aqueous
cured products are satisfactory here. environments, while peroxide cures are resistant.
In a 1986 review, Logothetis[31] summarized dif- Peroxide-curable perfluoroelastomers with en-
ferences in fluid and thermal resistance of TFE/ hanced heat resistance have recently been devel-
PMVE perfluoroelastomer vulcanizates cured with oped by Ausimont (now Solvay Solexis) workers,
three different cure systems, using three different using new branching and pseudo-living radical
cure-site monomers. The polymers evaluated had microemulsion polymerization technology.[32] In this
about the same major monomer composition, and the semibatch process, a perfluorinated diiodide modi-
vulcanizates had about the same initial properties fier, I(CF2)6I, is used as described in Sec. 4.6.1 to
after post cure: M100 = 6.5–8.0 MPa, TB = 13–16 make a narrow molecular weight distribution poly-
MPa, and EB = 140%–160%; Shore A Hardness = mer with iodine on most chain ends. In addition, a
80. Listed in Table 5.8 are changes in tensile strength fluorinated diolefin, CH2=CH–(CF2)6–CH=CH2,
after heat-aging in air for 10 days at various tem- is incorporated to get significant branching. The re-
peratures and the swell in various fluids after 70- sulting polymer has more than two iodine groups per
hour exposures. chain and considerable pendant vinyl groups. This
Triazine crosslinks from –RfCN cure sites are perfluoroelastomer, possibly precompounded with
exceptionally stable to heat-aging in air, being unaf- additional fluorinated diolefin, can be cured with per-
fected up to 290°C. At this temperature, tensile oxide only (no added TAIC radical trap) to produce
strength increases initially, then levels off on further vulcanizates with good long-term stability up to
exposure. This vulcanizate has reasonable service 290°C.[33]

��������� Heat Aging and Fluid Swell of Perfluoroelastomer Vulcanizates[31]

��������� –���� –� –����

Probable cure site monomer 8-CNVE VDF BTFB
Curative Ph4Sn Bisphenol TAIC
Heat Aging (% change in TB after aging 10 days in air at temperature )
225ºC -3 -11
250ºC -24 -54
275ºC -45 -80
290ºC +24 -36
Fluid Resistance (% swell after 70-hour exposure)
Conc. nitric acid, 85ºC 3 8 9
Glacial acetic acid, 100ºC 3 32 16
Butyraldehyde, 70ºC 13 10 14
Methyl ethyl ketone, 70ºC 6 4 4
Toluene, 100ºC 7 7 7
Water, 225ºC 10 60 7
5 CURE SYSTEMS FOR FLUOROELASTOMERS 95

A number of improvements have been reported to aromatic solvents compared to available VDF-
recently for nitrile-containing perfluoroelastomers. containing fluoroelastomers. The excellent resistance
Better processing polymers have been obtained with of TFE/P elastomers to polar solvents and to amines
initiation of polymerization by persulfate thermal and inorganic bases was not considered to be im-
decomposition.[34] The resulting carboxyl (-COOH) portant enough to offset the deficiencies, so DuPont
and carboxylate (-COO-) end groups form ionic clus- did not offer the product commercially. However,
ters that are much less stable than those involving Asahi Glass continued to develop polymerization and
sulfonate ends. In a further improvement, carboxy- curing systems, introducing TFE/P copolymer as
late end groups can be removed by pyrolysis at Aflas® in the mid-1970s. Much of the polymer has
250°C-325°C to get low-viscosity polymers that are been used in Japanese wire and cable coating appli-
readily mixed to obtain compounds with good flow cations because of its excellent electrical proper-
characteristics for extrusion and molding.[35] The ties. Use in elastomer fabricated parts has been rela-
cyano cure sites have been found to be quite versa- tively low, but increasing recently because of need
tile, allowing curing with certain nitrogen-containing for base-resistant fluoroelastomers.
nucleophilic compounds,[36] with ammonium salts of To minimize transfer reactions to propylene (and
organic or inorganic acids,[37] or with ammonia-gen- small amounts of propane in the monomer), Asahi
erating compounds.[38] Apparently, in most of these Glass workers developed a redox initiation system
cases, stable triazine crosslinks are formed after long to allow polymerization at low temperature (near
high-temperature post cures. 25°C).[42] The initiation system, consisting of am-
Nitrile-containing perfluoroelastomers are also monium persulfate, ferrous sulfate, ethylene diamine
curable with peroxide and radical trap. Ojakaar[39] tetraacetic acid (EDTA), and sodium hydroxy-
discloses curing of TFE/PMVE/8-CNVE perfluoro- methanesulfinate, allows attainment of number av-
elastomer with α,α´-bis(t-butylperoxy)diisopropyl- erage molecular weights above 100,000 Daltons.
benzene peroxide, trimethallyl isocyanurate Sulfate ion radicals are formed from the oxidation
crosslinker, and 1,8-bis(methylamino)naphthalene of ferrous ion by persulfate in a fast reaction. Ferric
organic base. Cure rates are much faster than those ions are in turn reduced back to ferrous ions by
with tetraphenyltin, and post curing can be carried hydroxymethanesulfinate in a rate-determining step
out at lower temperatures for shorter times. The involving hydroxide ion. EDTA forms complexes with
peroxide-cured perfluoroelastomers have better re- ferric and ferrous ions, so that they do not destabi-
sistance to hot water and ethylene diamine than that lize the polymer dispersion. Perfluorocarbon surfac-
of the same polymers cured with tetraphenyltin. tants and a buffer system (disodium hydrogen phos-
Apparently, hydrocarbon radicals on TMAIC moi- phate and sodium hydroxide, to maintain pH in the
eties add to –RfCN groups on polymer chains to form range 5.5 to 10) are used to stabilize the dispersion.
stable crosslinks. Reactor pressure is maintained at about 2.5 MPa
with a monomer mixture rich in TFE to attain rea-
sonable reaction rates.
5.5 � TFE/Propylene The isolated TFE/P dipolymer is subjected to a
heat treatment to generate enough unsaturation to
Elastomers: Peroxide, allow peroxide curing.[43] The Asahi Glass heat treat-
Bisphenol ment is carried out in the presence of air at tem-
peratures high enough to start polymer degradation,
In the 1960s, workers at DuPont[40] and Asahi typically 300°C to 360°C for 2 to 4 hours. Time and
Glass[41] found that TFE and propylene can be co- temperature are chosen to get significant modifica-
polymerized in alternating fashion to form fluoroelas- tion without excessive reduction of molecular weight.
tomers. Early attempts to cure TFE/P elastomers Besides allowing curing, the unsaturation and car-
with various incorporated cure-site monomers did bonyl groups formed enhance adhesion of the elas-
not produce commercially satisfactory vulcanizates. tomer to substrates such as metal and cloth. The
Also, elastomer processors regarded the material as efficiency of the heat treatment may be enhanced
deficient in such properties as compression set re- by addition of a metal oxide such as magnesium ox-
sistance, low-temperature flexibility, and resistance ide. In a patent example, a copolymer with compo-
96 FLUOROELASTOMERS HANDBOOK

sition TFE/P = 55/45 mole % and number average were described at a 1989 ACS Rubber Division
molecular weight 180,000 Daltons was mixed with meeting.[49] Resistance to automotive motor oils was
0.5 phr MgO and heated at 300°C for 2 hours in air compared to that of bisphenol-cured VDF/HFP di-
in an electric oven to obtain the modified fluoroelas- polymer and peroxide-cured VDF/HFP/TFE terpoly-
tomer. This was compounded with 5 phr a,a´-bis(t- mer; representative results are shown in Table 5.10.
butylperoxy)-p-diisopropyl benzene, 3 phr triallyl All polymers were compounded with 30 phr MT
isocyanurate, and 25 phr MT carbon black. After a black filler and press cured 12 minutes at 177°C.
press cure of 30 minutes at 160°C and oven post The bisphenol compounds were post cured at 230°C,
cure of 1 hour at 160°C, 1 hour at 180°C, and 2 the peroxide compound at 200°C for 16 hours.
hours at 200°C, the following vulcanizate physical Both VDF/HFP/(TFE) vulcanizates had surface
properties were obtained: M100 = 3.1 MPa, TB = 18.1 cracks after this oil exposure. The bisphenol-cured
MPa, EB = 260%, hardness (JIS-A) = 70, and com- TFE/P/VDF elastomer shows significantly better
pression set = 22% after 22 hours at 200°C. resistance to lubricating oils than that of VDF/HFP-
Typical properties of a heat-treated TFE/P di- containing elastomers. In a later review of the com-
polymer cured with peroxide and radical trap are mercial 3M product, Fluorel® II, Hull[50] recommends
listed in Table 5.9.[44] The compound was press cured the bisphenol-cured TFE/P/VDF terpolymer for ser-
30 minutes at 160°C and post cured 2 hours at 200°C. vice in automotive engine oils, transmission fluids,
Compared to VDF/HFP/TFE fluoroelastomers, and gear lubricants, but not for aqueous environ-
TFE/P dipolymer vulcanizates have poorer low- ments. A peroxide-cured terpolymer is recom-
temperature characteristics and resistance to com- mended for service in engine coolants. These VDF-
pression set. With their lower fluorine content containing terpolymers have better processing and
(55%–57%), TFE/P vulcanizates exhibit high swell curing characteristics than TFE/P dipolymers, but
in hydrocarbons, especially mixtures containing aro- base resistance is significantly compromised by the
matics, but are resistant to aqueous fluids and polar presence of the large fraction of VDF units. Base
solvents. resistance of TFE/P/VDF vulcanizates is generally
To obtain higher fluorine content and better cur- similar to that of VDF/PMVE/TFE elastomers,
ing characteristics, terpolymers of TFE and propy- which have better low-temperature characteristics.
lene with VDF have been made. During the early In the late 1990s, workers at DuPont Dow Elas-
1970s, DuPont workers made terpolymers contain- tomers re-investigated the TFE/P elastomer family
ing 5–26 mole % VDF, 50–65 mole % TFE, and 20– to develop fully base-resistant products with better
45 mole % P that were curable with diamine car- processing and curing characteristics. Terpolymers
bamate crosslinkers and quaternary ammonium or of TFE and propylene with small amounts of cer-
phosphonium accelerators.[45] In later work at Asahi tain cure-site monomers allowing practical bisphe-
Glass, aqueous dispersions of terpolymers contain- nol cures have been developed. [51] A preferred
ing 25–35 mole % VDF, about 40 mole % TFE, and version is a terpolymer containing 73 wt % TFE,
25–35 mole % P were treated with sodium hydrox- 23 wt % P, and 4 wt % trifluoropropylene (TFP),
ide before isolation of the polymer, to generate double CF3–CH=CH2. TFP is incorporated as isolated units
bonds used for curing with peroxide and radical flanked by TFE units. Dehydrofluorination results in
trap,[46] or with bisphenol and quaternary ammonium –CF2–CF2–CH2–C(CF3)=CF–CF2– structures
or phosphonium salts.[47] Further improvements in to which nucleophiles can attach to form crosslinks.
bisphenol curing of TFE/P/VDF terpolymers were Highly reactive accelerators are desirable to get good
made at 3M by Grootaert and Kolb,[48] who found cure rates. A preferred compound includes as the
more effective accelerators for polymers contain- curative/accelerator combination methyltributyl-
ing high levels of VDF. The preferred polymer com- ammonium Bisphenol AF salt (1:1 molar ratio) along
position is in the range 30–36 mole % VDF, 41–45 with calcium hydroxide, active magnesium oxide, and
mole % TFE, and 19–28 mole % P (thus about 58%– fillers. This product has much better base resistance
60% fluorine), cured with Bisphenol AF and than VDF-containing terpolymers, and better hydro-
tributyl(2-methoxy)propyl phosphonium chloride. carbon fluid resistance than TFE/P dipolymers be-
Vulcanizate properties of a precommercial version cause of its higher fluorine content (58%).[52]
5 CURE SYSTEMS FOR FLUOROELASTOMERS ­ 97

Table 5.9 Properties of TFE/P Dipolymer Vulcanizate[44] ­

Heat-Treated Polymer
Specific gravity 1.55
Mooney viscosity, ML-10 (100ºC) 85
Appearance Dark Brown
Formulation, phr
Polymer 100
á,á´-bis(t-butylperoxy)-p-diisopropyl benzene 2
Triallylisocyanurate 3
MT carbon black (N-908) 30
Vulcanizate Properties
Specific gravity 1.60
Stress/strain at 25ºC
M100, MPa 3
TB, MPa 20
EB, % 300
Compression set at 200ºC, %
After 1 day 40
After 30 days 65
Hardness, Durometer A 72
Low-temperature characteristics
Brittle Point, ºC -40
Retraction temperature, TR-10, ºC 3
Volume increase after fluid immersion, %
95% Sulfuric acid, 3 days at 100ºC 4.4
Water, 3 days at 150ºC 8.7
Steam, 3 days at 160ºC 4.6
Fuel Oil B, 7 days at 25ºC 59
Benzene, 7 days at 25ºC 40
Methanol, 7 days at 25ºC 0.2
Ethyl acetate, 7 days at 25ºC 88
98 FLUOROELASTOMERS HANDBOOK

Table 5.10 Comparison of TFE/P/VDF with VDF/HFP/(TFE) Elastomers[49]

Polymer VDF/HFP VDF/HFP/TFE/Br-CSM TFE/P/VDF

% Fluorine 66 70 59
Cure system BpAF Peroxide BpAF
ODR at 177ºC
ML, N·m 1.0 3.3 1.1
MH, N·m 7.9 11.3 8.9
ts0.2, minutes 1.7 1.1 2.7
tc90, minutes 4.0 5.9 5.8
Stress/strain
M100, MPa 3.6 5.3 5.1
TB, MPa 13.7 14.3 15.2
EB, % 286 219 235
Hardness, Shore A 75 76 74
% Change in properties after exposure to 10W/30 SG/CC motor oil, 168 h at 160ºC
M100 +29 +31 +9
TB -63 -32 -38
EB -59 -40 -17

In a recent update to his previous studies (dis- inefficient as a cure-site monomer in TFE/P copoly-
cussed in Secs. 5.1.2 and 5.2, Refs. 9 and 10), mers. The remaining unsaturation formed by base
Schmiegel[53] used high-resolution 377 MHz 19F attack is not susceptible to nucleophilic addition, so
NMR to study the reactions of TFE/P copolymers vulcanizates do not fail by surface cracking or
with the organic base DBU in solution. Treatment embrittlement. However, such unsaturation is sus-
of terpolymer with TFE/P/VDF = 54/14/32 wt % = ceptible to hydrolysis and network breakdown, es-
39/24/37 mole % in deuterated tetrahydrofuran so- pecially in hot aqueous environments. In contrast,
lution with excess DBU gives considerable reaction TFE/P/TFP terpolymers show attack by DBU only
at VDF sites with elimination of HF, as shown in at the TFP site, with little HF evolution, as shown in
Fig. 5.10, similar to reactions observed with VDF/ Fig. 5.11. The bulk of the polymer shows no change,
TFE dipolymers in the previous study. Only part of as shown in Fig. 5.12. Thus this cure-site monomer
these reactions is at TFE/VDF/TFE sites that may allows curing without base attack on the bulk of the
be usable in curing. Thus, the NMR study is consis- main chain of the terpolymer. The deleterious effect
tent with the need to incorporate high VDF levels of increasing VDF content on oil resistance of TFE/
(>10%) to get acceptable curing. VDF is relatively P copolymers is shown in Fig. 5.13.
5 CURE SYSTEMS FOR FLUOROELASTOMERS 99

Figure 5.10 DBU Treatment of TFE/P/VDF Figure 5.13 Base resistance of TFE/P/VDF
Terpolymer[53] elastomers.[53] Effect of weight % content of vinylidene
fluoride on polymer base resistance: Change in Eb
after aging in ASTM Reference Oil 105 @ 150°C.

5.6 � Ethylene/TFE/PMVE
Elastomers: Peroxide,
Bisphenol
Ethylene/TFE/PMVE (ETP) elastomers were
developed during the early 1980s for severe service
in oil field, aerospace, and automotive applications.[54]
ETP was designed to have better resistance to po-
lar fluids and base than that of VDF/HFP/TFE and
VDF/PMVE/TFE elastomers, and better low-tem-
perature flexibility and resistance to hydrocarbons
than that of TFE/P elastomers. A bromine-contain-
Figure 5.11 Attack of DBU on TFP Site[53] ing cure-site monomer (BTFB) is incorporated in
commercial ETP polymers to allow peroxide curing
with TMAIC or TAIC radical trap. Patent
examples[55] of polymers that appear to approximate
commercial offerings have composition in the range
E/TFE/PMVE/BTFB = 7.8-6.7/43.6–47.4/46.9–
44.0/1.7–1.9 wt % = 27.7–24.1/43.3–48.1/28.2–26.9/
0.8–0.9 mole %. This composition contains about
66% fluorine and 1% hydrogen, similar to that of
commercial high-fluorine VDF/TFE/PMVE/BTFB
types like Viton® GFLT (see Sec. 5.3 and Table 5.6).
Compounding, processing, and curing recom-
mendations for the commercial products, Viton Ex-
treme ETP-500 and ETP-900, are given in a recent
ACS paper,[56] along with property comparisons with
other fluoroelastomers. Compounding is generally
similar to that for VDF-containing polymers like
Figure 5.12 Treatment of TFE/P/TFP Terpolymer[53] GFLT, with some adjustments necessary for service
100 FLUOROELASTOMERS HANDBOOK

in aggressive fluids. TAIC (1 to 4 phr) and TMAIC These results show the good resistance of ETP
(0.7 to 3 phr) are recommended as radical traps. vulcanizates to a wide range of fluids, including
TMAIC may give somewhat better compression set amine-containing lubricants and aqueous that
and heat aging characteristics. Luperco 101XL or degrade VDF/HFP elastomers, polar solvents
130XL are satisfactory peroxides. Litharge (PbO) which swell VDF/HFP elastomers excessively,
or zinc oxide gives good fluid and heat resistance. and aromatic solvents that severely swell TFE/P elas-
MT black is the filler of choice. Other carbon blacks tomer.
may be used, but furnace blacks may interfere with Recently, Schmiegel and Tang[57] have incorpo-
peroxide curing and cause mold sticking. Mineral rated low levels of trifluoropropylene (TFP), CF3–
fillers such as Blanc Fixe (BaSO4) may be used; CH=CH2, or 2H-pentafluoropropylene (2H-PFP),
other mineral fillers may not be compatible with ser- CF2=CH–CF3, into ETP elastomers to allow bisphe-
vice in aggressive fluids such as aqueous base. Heat nol curing. Effective curing is obtained with Bisphe-
resistance of ETP vulcanizates is generally similar nol AF and tetrabutylammonium hydrogen sulfate
to that of other peroxide-cured fluoroelastomers, with or with methyltributylammonium Bisphenol AF salt
long-term service possible at temperatures up to (1:1 molar ratio). Calcium hydroxide and magnesium
230°C. ETP is compared to other fluoroelastomers oxide are used to take up water and HF generated.
in compounds with 30 phr MT black (N990), cured Press cure and post cure conditions are similar to
to give medium hardness vulcanizates with good those used for other bisphenol-cured fluoroelas-
physical strength and elongation. Molded slabs were tomers. The resulting bisphenol vulcanizates have
cut into dumbbells for testing in various fluids. Re- better compression set resistance than that of per-
sults are shown in Table 5.11 as changes in tensile oxide vulcanizates of bromine-containing polymers,
strength and volume from original properties after and retain the excellent fluid resistance of ETP.
immersion for 168 hours.

Table 5.11 Fluid Resistance of ETP and Other Fluoroelastomers[56]

Fluoroelastomer A401C GF 100H ETP-500

Composition VDF/HFP VDF/HFP/TFE TFE/P E/TFE/PMVE
% Fluorine 66 70 57 67
Cure Bisphenol TAIC TAIC TAIC
Property change after fluid exposure, 168 h
80W/90 EP gear lube, 150ºC
% TB change -37 -53 -8 -6
% Volume swell 1 3 6 2
Toluene, 40ºC
% TB change -40 -27 -65 -21
% Volume swell 23 11 64 9
Methyl ethyl ketone, 23ºC
% TB change -91 -86 -66 -34
% Volume swell 222 183 77 19
30% Potassium hydroxide, 100ºC
% TB change -95 -92 +12 -8
% Volume swell 132* 12* 1 6
*Sample disintegrating
5 CURE SYSTEMS FOR FLUOROELASTOMERS 101

REFERENCES �
1. �Arnold, R. G., Barney, A. L., and Thompson, D. C,�Rubber Chemistry and Technology, 46:631 (Jul
1973) �
2 Moran, A. L., and Pattison, D. B., Rubber World, 103:37 (1971) �
3. �Pattison, D. B., US Patent 3,876,654, assigned to DuPont Co. (1975)
4. �Gladding, E. K., and Nyce, J. L., US Patent 3,707,529, assigned to DuPont Co. (Dec 26, 1972)
5. �Moore, A. L., US Patent 3,839,305, assigned to DuPont Co. (Oct 1, 1974)
6. �Logothetis, A. L., “Fluoroelastomers,” Organofluorine Chemistry: Principles and Commercial
Applications (R. E. Banks, et al., eds.), p. 381, Plenum Press, New York (1994)
7. �Fogiel, A. W., Polymer Symposium, J. Polymer Science 53:333 (1975)
8. �DuPont Product Information Bulletin VT-220.A401C (Nov, 1992)
9. �Schmiegel, W. W., Kautschuk Gummi Kunstoffe, 31:137 (1978)
10. �Schmiegel, W. W., Die Angewandte Makromolekulare Chemie, 76/77:39–65 (1979)
11. �Moggi, G. and Mancini, L., US Patent 4,259,463, assigned to Montedison S.p.a. (Mar 31, 1981)
12. �Moggi, G., US Patent 4,501,858, assigned to Montedison S.p.a. (Feb 26, 1985)
13. �Carlson, D. P., and Schmiegel, W. W., US Patent 4,957,975, assigned to DuPont Co. (Sep 18, 1990)
14. �D. Apotheker and P. J. Krusic, US Patent 4,035,565, assigned to DuPont Co. (Jul 12, 1977)
15. �Tatemoto, M., and Morita, S., US Patent 4,361,678, assigned to Daikin Kogyo Co. (Nov 30, 1982)
16. �Moore, A. L., US Patent 4,973,633, assigned to DuPont Co. (Nov 27, 1990)
17. �Apotheker, D., Finlay, J. B., Krusic, P. J., and Logothetis, A. L., Rubber Chemistry and Technology,
55:1004–1018 (Sep-Oct, 1982)
18. �DuPont Product Information Bulletin VT-240.GBL-900 (May 1993)
19. �Okumoto,T., Ichikawa, M., and Terashima, K., Nippon Gomu Kyokaishi, 4:248 (1985); translation in
International Polymer Science and Technology, 12(8):65 (1985)
20. �Bowers, S., “A New Series of Peroxide Curable Specialty Fluoroelastomers with Significant
Improvements in Processability and Physical Properties,” paper given at Brazilian Rubber Congress,
Sao Paulo, Brazil (Nov 6–7, 2001)
21. �DuPont Product Information Bulletin VT-250.GFLT-300/301 (May, 1993)
22. �Bowers, S., and Schmiegel, W. W., US Patent 6,329,469, assigned to DuPont Dow Elastomers LLC
(Dec 11, 2001)
23. �Pattison, D. B., US Patent 3,467,638, assigned to DuPont Co. (Sep 16, 1969)
24. �Barney, A. L., and Honsberg, W., US Patent 3,580,889, assigned to DuPont Co. (May 25, 1971)
25. �Schroeder, H. E., Rubber Chemistry and Technology 57:G100 (Jul–Aug 1984)
26. �Carlson, D. P., and Schmiegel, W. W., “Fluoropolymers, Organic,” in: Ullmann’s Encyclopedia of
Industrial Chemistry, Fifth Edition, A11:424, VCH Verlagsgesellschaft mbH, Weinheim, Germany (1988)
27. �Finlay, J. B., US Patent 4,529,784, assigned to DuPont Co. (Jul 16, 1985)
28. �Breazeale, A. F., US Patent 4,281,092, assigned to DuPont Co. (Jul 28, 1981)
29. �Logothetis, A. L., “Novel Perfluoroelastomers,” paper given at Centenary of the Discovery of Fluorine
International Symposium, Paris, France (Aug 25–29, 1986)
30. �Logothetis, A. L., US Patent 4,948,853, assigned to DuPont Co. (Aug 14, 1990)
102 FLUOROELASTOMERS HANDBOOK

31. �Logothetis, A. L., “Novel Fluoroelastomers,” paper presented at International Fluorine Symposium,
Paris, France (Aug 25–29, 1986)
32. �Ferro, R., Arcella, V., Albano, M., Apostolo, M. and Wlassics, I , “New Developments in Polymerization
Technologies and Curing,” paper presented at International Rubber Conference, Manchester, UK (Jun
1999)
33. �Anonymous, Tecnoflon PFR 95 Solvay Solexis Product Data Sheet (Dec 2002)
34. �Coughlin, M. C., and Manaco, C. D., US Patent 5,789,489, assigned to DuPont Dow Elastomers LLC
(Aug 4, 1998)
35. �Schmiegel, W. W., US Patent 5,789,509, assigned to DuPont Dow Elastomers LLC (Aug 4, 1998)
36. �C. J. Bish, P. A. Morken, and W. W. Schmiegel, US Patent Application Publication No. US 2002/
0026014 (Feb 28, 2002)
37. �Kumiya, F., Saito, S., and Tatsu, H., US Patent 5,565,512, assigned to Nippon Mektron, Limited (Oct
15, 1996)
38. �MacLachlan, J. D., Morken, P. A., Schmiegel, W. W., and Takahashi, K., US Patent 6,281,296,
assigned to DuPont Dow Elastomers LLC (Aug 28, 2001)
39. �Ojakaar, L., US Patent 4,983,680, assigned to DuPont Co. (Jan 8, 1991)
40. �Brasen, W. R., and Cleaver, C. S., US Patent 3,467,635, assigned to DuPont Co. (Sep 16, 1969)
41. �Tabata, Y., Ishigure, K., and Sobue, H., J. Poly. Sci., A-2:2235 (1964)
42. �Kojima, G., and Hisasue, M., Makromol. Chemie 182:1429–1439 (1981)
43. �Morozumi, M., Kojima, G., and Abe, T., US Patent 4,148,982, assigned to Asahi Glass Co. Ltd. (Apr
10, 1979)
44. �Kojima, G., Kojima, H., and Tabata, Y., Rubber Chem. Technol. 50:403 (1977).
45. �Harrell, J. R., and Schmiegel, W. W., US Patent 3,859,259, assigned to DuPont Co. (Jan 7, 1975)
46. �Wachi, H., Kaya, S., and Kojima, G., US Patent 4,645,799, assigned to Asahi Glass Co., Ltd. (Feb 24,
1987)
47. �Ito, Y., and Wachi, H., US Patent 4,758,618, assigned to Asahi Glass Co., Ltd. (Jul 19, 1988)
48. �Grootaert, W. M. A., and Kolb, R. E., US Patent 4,882,390, assigned to Minnesota Mining and
Manufacturing Co. (Nov 21, 1989)
49. �Grootaert, W. M., Kolb, R. E., and Worm, A. T., “A Novel Fluorocarbon Elastomer for High-Temperature
Sealing Applications in Aggressive Motor Oil Environments,” paper presented at ACS Rubber Division
meeting, Detroit, Michigan (Oct 17-20, 1989)
50. �Hull, D. E., Automotive Polymers & Design, pp. 18–21 (June, 1990)
51. �Bauerle, J. G., and Schmiegel, W. W., US Patent Application Publication No. US 2003/0065132 (Apr 3,
2003)
52. �Bauerle, J. G. and Tang, P. L., SAE World Congress, Detroit, Michigan (Mar. 2002)
53. �Schmiegel, W. W., “A Review of Recent Progress in the Design and Reactions of Base-Resistant
Fluoroelastomers,” paper presented at International Rubber Conference, Nurenberg, Germany (Jun
30–Jul 3, 2003)
54. �Moore, A. L., Elastomerics, pp. 14–17 (Sep, 1986)
55. �Moore, A. L., US Patent 4,694,045, assigned to DuPont Co. (Sep 15, 1987)
56. �Stevens, R. D., and Moore, A. L. “A New, Unique Viton® Fluoroelastomer With Expanded Fluids
Resistance,” paper presented at ACS Rubber Division meeting, Cleveland, Ohio (Oct 21–24, 1997)
57. �Schmiegel, W. W., and Tang, P. L., US Patent Application Publication No. US 2003/0004277 (Jan 2, 2003)