Note: Descriptions are shown in the official language in which they were submitted.
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CURABLE PARTIALLY FLUORINATED POLYMER COMPOSITIONS
TECHNICAL FIELD
[0001] Curing of compositions comprising a partially fluorinated amorphous
fluoropolymer substantially free of iodine, bromine and nitrile cure sites
with a curing
agent comprising a terminal olefin with at least one olefinic hydrogen are
disclosed.
SUMMARY
[0002] There is a desire to identify a novel curing system for partially
fluorinated
amorphous fluoropolymers.
[0003] In one aspect, a curable partially fluorinated polymer is disclosed
comprising:
(i) a partially fluorinated amorphous fluoropolymer, wherein the partially
fluorinated amorphous fluoropolymer comprises carbon-carbon double bonds or is
capable
of forming carbon-carbon double bonds along the partially fluorinated
amorphous
fluoropolymer, wherein the partially fluorinated amorphous fluoropolymer is
substantially
free of bromine, iodine, and nitrile; and
(ii) a curing agent comprising a terminal olefin with at least one olefinic
hydrogen.
[0004] In another aspect, an article comprising the cured composition
described above is
disclosed.
[0005] In yet another aspect a method of making a partially fluorinated
elastomer is
disclosed comprising curing the curable partially fluorinated polymer
composition
disclosed above.
[0006] The above summary is not intended to describe each embodiment. The
details of
one or more embodiments of the invention are also set forth in the description
below.
Other features, objects, and advantages will be apparent from the description
and from the
claims.
DETAILED DESCRIPTION
[0007] As used herein, the term
"a", "an", and "the" are used interchangeably and mean one or more; and
"and/or" is used to indicate one or both stated cases may occur, for example A
and/or B includes, (A and B) and (A or B);
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"backbone" refers to the main continuous chain of the polymer;
"crosslinking" refers to connecting two pre-formed polymer chains using
chemical
bonds or chemical groups;
"cure-site" refers to functional groups, which may participate in
crosslinking; and
"interpolymerized" refers to monomers that are polymerized together to form a
polymer backbone; and
"polymer" refers to macromolecules made up of large numbers (e.g., hundreds or
more) of interpolymerized monomer units and have high molecular weight (e.g.,
more
than 10,000, 20,000, 50,000 or even 100,000 grams/mole).
Also herein, recitation of ranges by endpoints includes all numbers subsumed
within that range (e.g., 1 to 10 includes 1.4, 1.9, 2.33, 5.75, 9.98, etc.).
[0008] Also herein, recitation of "at least one" includes all numbers of one
and greater
(e.g., at least 2, at least 4, at least 6, at least 8, at least 10, at least
25, at least 50, at least
100, etc.).
[0009] In the present disclosure, it has been found that a partially
fluorinated amorphous
fluoropolymer substantially free of bromine, iodine, and nitrile groups can be
cured with a
compound comprising a terminal olefin with at least one olefinic hydrogen.
[0010] Fluoropolymer
[0011] The amorphous fluoropolymers of the present disclosure are partially
fluorinated
polymers. As disclosed herein, an amorphous partially fluorinated polymer is a
polymer
comprising at least one carbon-hydrogen bond and at least one carbon-fluorine
bond on
the backbone of the polymer. In one embodiment, the amorphous partially
fluorinated
polymer is highly fluorinated, wherein at least 60, 70, 80, or even 90% of the
polymer
backbone comprises C-F bonds.
[0012] The amorphous fluoropolymer of the present disclosure also comprises
carbon-
carbon double bonds and/or is capable of forming carbon-carbon double bonds
along the
polymer chain. In one embodiment, the partially fluorinated amorphous
fluoropolymer
comprises carbon-carbon double bonds along the backbone of the partially
fluorinated
amorphous fluoropolymer or is capable of forming carbon-carbon double bonds
along the
backbone of the partially fluorinated amorphous fluoropolymer. In another
embodiment,
the partially fluorinated amorphous fluoropolymer comprises carbon-carbon
double bonds
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or is capable of forming carbon-carbon double bonds in a pendent group off of
the
backbone of the partially fluorinated amorphous fluoropolymer.
[0013] The fluoropolymer capable of forming carbon-carbon double bonds means
that the
fluoropolymer contains units capable of forming double bonds. Such units
include, for
example, two adjacent carbons, along the polymer backbone or pendent side
chain,
wherein a hydrogen is attached to the first carbon and a leaving group is
attached to the
second carbon. During an elimination reaction (e.g., thermal reaction, and/or
use of acids
or bases), the leaving group and the hydrogen leave forming a double bond
between the
two carbon atoms. An exemplary leaving group includes: a fluoride, an
alkoxide, a
hydroxide, a tosylate, a mesylate, an amine, an ammonium, a sulfide, a
sulfonium, a
sulfoxide, a sulfone, and combinations thereof
[0014] The amorphous fluoropolymer comprises a plurality of these groups
(carbon-
carbon double bonds or groups capable of forming double bonds) to result in a
sufficient
cure. Generally, this means at least 0.1, 0.5, 1, 2, or even 5 mol%; at most
7, 10, 15, or
even 20 mol % (i.e., moles of these carbon-carbon double bonds or precursors
thereof per
mole of polymer).
[0015] In one embodiment, the amorphous partially fluorinated polymer is
derived from at
least one hydrogen containing monomer such as vinylidene fluoride.
[0016] In one embodiment, the amorphous fluoropolymer comprises adjacent
copol y in erized units of vinylidene fluoride (VDF) and hexafluoropropylene
(1117P)
copolymerized units of VDF (or tetratluoroetlaylene) and a fluorinated
comonomer
capable of delivering an acidic hydrogen atom to the polymer backbone, such as
trifluoroethylene; vinyl fluoride; 3,3,3-trifluoropropene-1;
pentafluoropropene (e.g., 2-
hydropentafluoropropylene and I-hydropentatluoropropylene); 2,3,3,3-
tetrat1uoropropene;
and combinations thereof.
[0017] In some embodiments, small amounts (e.g., less than 10, 5, 2, or even 1
wt%) of
additional monomers may be added so long as the amorphous fluoropolymer is
able to be
cured using the curing agent disclosed herein.
[0018] In one embodiment, the amorphous fluoropolymer is additionally derived
from a
hydrogen containing monomer including: pentafluoropropylene (e.g., 2-
hydropentafluropropylene), propylene, ethylene, isobutylene, and combinations
thereof
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[0019] In one embodiment, the amorphous fluoropolymer is additionally derived
from a
perfluorinated monomer. Exemplary perfluorinated monomers include:
hexafluoropropene; tetrafluoroethylene; chlorotrifluoroethylene;
perfluoro(alkylvinyl
ether) such as perfluoromethyl vinyl ether, CF2=CFOCFCF2CF20CF3,
CF2=CFOCF20CF2CF2CF3, CF2=CFOCF20CF2CF3, CF2=CFOCF20CF3, and
CF2=CFOCF20C3F7, perfluoro(alkylally1 ether) such as perfluoromethyl allyl
ether,
perfluoro(alkyloxyally1 ether) such as perfluoro-4,8-dioxa-1-nonene (i.e.,
CF2=CFCF20CF2)30CF3], and combinations thereof.
[0020] Exemplary types of polymers include those comprising interpolymerized
units
derived from (i) vinylidene fluoride, tetrafluoroethylene, and propylene; (ii)
vinylidene
fluoride, tetrafluoroethylene, ethylene, and perfluoroalkyl vinyl ether, such
as
perfluoro(methyl vinyl ether); (iii) vinylidene fluoride with
hexafluoropropylene; (iv)
hexafluoropropylene, tetrafluoroethylene, and vinylidene fluoride; (v)
hexafluoropropylene and vinylidene fluoride, (vi) vinylidene fluoride and
perfluoroalkyl
vinyl ether; (vii) vinylidene fluoride, tetrafluoroethylene, and
perfluoroalkyl vinyl ether,
(viii) vinylidene fluoride, perfluoroalkyl vinyl ether,
hydropentafluoroethylene and
optionally, tetrafluoroethylene; (ix) tetrafluoroethylene, propylene, and
3,3,3-
trifluoropropene; (x) tetrafluoroethylene, and propylene; (xi) ethylene,
tetrafluoroethylene,
and perfluoroalkyl vinyl ether, and optionally3,3,3-trifluoropropylene; (xii)
vinylidene
fluoride, tetrafluoroethylene, and perfluoroalkyl allyl ether, (xiii)
vinylidene fluoride and
perfluoroalkyl allyl ether; (xiv) ethylene, tetrafluoroethylene, and
perfluoroalkyl vinyl
ether, and optionally3,3,3-trifluoropropy1ene; (xv) vinylidene fluoride,
tetrafluoroethylene,
and perfluoroalkyl allyl ether, (xvi) vinylidene fluoride and perfluoroalkyl
allyl ether;
(xvii) vinylidene fluoride, tetrafluoroethylene, and perfluoroalkyloxyallyl
ether, (xviii)
vinylidene fluoride and perfluoroalkyloxyallyl ether; (xiv) vinylidene
fluoride,
tetrafluoroethylene, and perfluoroalkyloxyallyl ether, (xv) vinylidene
fluoride and
perfluoroalkyloxyallyl ether; and (xvi) combinations thereof
[0021] Advantageously, by using the curing agent disclosed herein, the
amorphous
fluoropolymers of the present disclosure can be cured without the need for
pendent
bromine, iodine, or nitrile cure sites along the polymer backbone. Often, the
iodine and
bromine-containing cure site monomers, which are polymerized into the
fluoropolymer
and/or the chain ends, can be expensive among other things.
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[0022] The amorphous fluoropolymer of the present disclosure is substantially
free of I,
Br, and nitrile groups, wherein the amorphous fluoropolymer comprises less
than 0.1,
0.05, 0.01, or even 0.005 mole percent relative to the total polymer.
[0023] In one embodiment, the amorphous fluoropolymers of the present
disclosure are
non-grafted, meaning that they do not comprise pendant groups including vinyl,
allyl,
acrylate, amido, sulfonic acid salt, pyridine, carboxylic ester, carboxylic
salt, hindered
silanes that are aliphatic or aromatic tri-ethers or tri-esters. In one
embodiment, the
amorphous fluoropolymer does not comprise a monophenol graft.
[0024] Curing Agent
[0025] The curing agent of the present disclosure is a compound containing at
least one
terminal olefin with at least one olefinic hydrogen. In other words, the
curing agent
comprises a terminal carbon-carbon double bond with at least one of the
carbons
comprising at least one hydrogen.
[0026] In one embodiment, the curing agent of the present disclosure is
represented by
Formula I:
CX1X2=CX3-R (I)
wherein Xi, X2, and X3 are independently selected from H, Cl, and F and at
least one of Xi,
X2, and X3 is H; R is a monovalent group.
[0027] R is a monovalent group comprising 1 to 20 carbon atoms, which can be
linear,
branched or cyclic. R may be aromatic, aliphatic, or comprise both an aromatic
and an
aliphatic portion. R may be non-fluorinated (comprising no fluorine atoms),
partially
fluorinated (comprising at least one C-H bond and at least one C-F bond, or
perfluorinated
(comprising no C-H bonds and at least one C-F bond).
[0028] In one embodiment, R comprises at least one catenated heteroatom such
as 0, S or
N (e.g., an ether linkage). In one embodiment, R comprises a terminal group
selected from
an alcohol (-OH), an amine (-NH2, -NHR, and ¨NRR' where R and R' are an
organic
group), a thiol (-SH), a carboxylic acid (-COOH), an olefin.
[0029] Exemplary R groups include: -0-R'-0-CX=CX2; -CX2-0-R'-0-CX=CX2; -CX2-
0-R'-0- CX2CX=CX2; -R'-OH; wherein R' is a partially fluorinated or non-
fluorinated
divalent group, and X is independently selected from H, Cl and F. R' comprises
an
alkylene group, a cylcoalkylene, an arylene group, or combination thereof
(e.g.,
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alkarylene) comprising at least 1, 2, 4, or even 6 carbon atoms and at most
30, 25, 20, or
even 15 carbon atoms.
[0030] The curing agent is a non-polymeric, small molecule, having a molecular
weight of
less than 2000, 1500, 1000, 500, 250, or even 175 g/mol.
[0031] In one embodiment, the curing agent is selected from at least one of a
divinyl and a
diallyl compound. In other words, a compound comprising at least two vinyl
moieties or at
least two allyl moieties. In one embodiment, the curing agent comprises a
vinyl moiety
and an allyl moiety.
[0032] In one embodiment, the curing agent comprises at least one
nonfluorinated
terminal olefin group. In one embodiment, the curing agent comprises a non-
aromatic
terminal olefin and/or non-aromatic alcohol. In one embodiment, the curing
agent
comprises at least one phenolic group.
[0033] Exemplary curing agent include:
= '
/
/ /H
0
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H
H H
(/¨) CF3 ()
H 0
H'"- \\Z....."..,\X 0 ___________________________ \
CF3
H
H H H H
H
- n
H F F
H
,,,,..\ H H H H
H \<1 H
H
H 0 0
n - n
F F F F
H H
H
H
F
/H
o
0
H F
F Rf
H H
H
H
F
F
0,_
H--
Rf ¨ N H H
F
)6(
0 H
F H H
F
F H
H F F F
\ F
H
0
n1\ N H
H ___________________________ /
:.'.5(Ho H / F
H H
H
H
o'''-H
Rf ¨N H
H
0 H
<H 1.......<
H<
H H H
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0
H
H._ H
}4
,µ
, . .4(
______________________________________ /*/ \\ ___________ H
0
CF3
and combinations thereof, where n is independently selected from an integer
from 1 to 50,
1 to 20, 1 to 10, or even 2 to 10, and Rf is a fluorinated alkyl group. Rf may
be partially or
fully fluorinated. In one embodiment, Rf may comprise catenated heteroatoms
such as 0,
S, or N. Rf may be linear or branched, saturated or unsaturated. In one
embodiment Rf is
a Cl to C12 fluorinated alkyl group (optionally, perfluorinated).
[0034] The curing agent should be used in quantities substantial enough to
cause the
amorphous fluoropolymer to cure, as indicated by a rise in torque on a moving
die
rheometer. For example, at least 1, 1.5, 2, 2.5, 3, or even 4 or more
millimoles per 100
parts of the amorphous fluoropolymer is used. If too little curing agent is
used, the
amorphous fluoropolymer will not cure. For example, no more than 20, 15, 10,
or even 8
millimoles of the curing agent per 100 parts of the amorphous fluoropolymer is
used. If
too much curing agent is used, the amorphous fluoropolymer can become brittle.
[0035] In one embodiment, the curable partially fluorinated polymer
composition is
substantially free of a monophenol, meaning that the composition comprising
the
amorphous fluoropolymer comprises less than 0.1, 0.01, or even 0.001 % moles
of
monophenol versus the moles of amorphous fluoropolymer.
[0036] Acid Acceptor
[0037] In one embodiment, an acid acceptor is used in the present disclosure,
such acid
acceptors include organic, inorganic, or blends of thereof. Examples of
inorganic
acceptors include magnesium oxide, lead oxide, calcium oxide, calcium
hydroxide, dibasic
lead phosphate, zinc oxide, barium carbonate, strontium hydroxide, calcium
carbonate,
hydrotalcite, etc. Organic acceptors include amines, epoxies, sodium stearate,
and
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magnesium oxalate. Particularly suitable acid acceptors include calcium
hydroxide,
magnesium oxide and zinc oxide. Blends of acid acceptors may be used as well.
The
amount of acid acceptor will generally depend on the nature of the acid
acceptor used.
[0038] In one embodiment, at least 0.5, 1, 2, 3, or even 4 parts of the acid
acceptor per 100
parts of the amorphous fluoropolymer are used. In one embodiment, no more than
10, 7, or
even 5 parts of the acid acceptor per 100 parts of the amorphous fluoropolymer
are used.
[0039] Onium Compound
[0040] In one embodiment, an organo onium compound is added to the composition
as a
phase transfer catalyst to assist with the crosslinking of the amorphous
fluoropolymer
and/or may be used to generate the double bonds on the fluoropolymer through
dehydrofluorination. Such organo onium compounds include quaternary ammonium
hydroxides or salts, quaternary phosphonium hydroxides or salts, and ternary
sulfonium
hydroxides or salts.
[00411 Briefly, a phosphonium and ammonium salts or compounds comprise a
central
atom of phosphorous or nitrogen, respectively, covalently bonded to four
organic moieties
by means of a carbon-phosphorous (or carbon-nitrogen) covalent bonds and is
ionically
associated with an anion. The organic moieties can be the same or different.
[0042] Briefly, a sulfonium compound is a sulfur-containing organic compound
in which
at least one sulfur atom is covalently bonded to three organic moieties having
from 1 to 20
carbon atoms by means of carbon-sulfur covalent bonds and is ionicaliy
associated with an
anion. The organic moieties can be the same or different. The sulfonium
compounds may
have more than one relatively positive sulfur atom, e.g. [(C6 H5)2 S'-
(CH2)4S+(C6H5)2]2C1-,
and two of the carbon-sulfur covalent bonds may be between the carbon atoms of
a
divalent organic moiety, i.e., the sulfur atom may be a heteroatom in a cyclic
structure.
[0043] The organo onium compounds suitable for use in this disclosure are
known and are
described in the art. See, for example, U.S. Pat. Nos. 5,262,490 (Ki.plb et
al.) and
4,912,171 (Grootaeit et al.), herein incorporated by reference.
[0044] Exemplary organo onium compounds include: C3-C6 symmetrical
tetraalkylammonium salts, unsymmetrical tetraalkylammonium salts wherein the
sum of
alkyl carbons is between 8 and 24 and benzyltrialkylammonium salts wherein the
sum of
alkyl carbons is between 7 and 19 (for example tetrabutylammonium bromide,
tetrabutylammonium chloride, benzyltributylammonium chloride,
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benzyltriethylammonium chloride, tetrabutylarnmonium hydrogen sulfate and
tetrabutyl ammonium hydroxide, phenyltrimethylammoniurn chloride,
tetrapentylammonium chloride, tetrapropylammonium bromide, tetrahexylammonim
chloride, and tetraheptylaminonium bromidetetrarnethylammonium chloride);
quaternary
phosphonium salts, such as tetrabutylphosphonium salts, tetraphenylphosphonium
chloride, benzyltriphertylphosphoniurn chloride, tributylallylphosphonium
chloride,
tributylbenzyl phosphoniurn chloride, tributy1-2-inethoxypropylphosphonium
chloride,
benzyldiphenyl(dirnethylamino)phosphonium chloride, 8-benzy1-1,8-
diazobicyclo[5.4.0]7-
undecenium chloride, benzyltris(dimethylarnino)phosphonium chloride, and
bis(benzyldiphenylphosphine)iminium chloride. Other suitable organo onium
compounds
include 1,8-diazabicyclo[5,4.0]undec-7-ene and 1,5-diazabicyclo[4.3,0]non-5-
ene,
Phenolate is a preferred anion for the quaternary ammonium and phosphonium
salts.
[0045] In one embodiment, the organo onium compound is used between 1 and 5
millimoles per 100 parts of the amorphous fluoropolymer (mmhr).
[0046] Peroxide
[0047] In one embodiment, the curable composition comprises a peroxide, used
to initiate
the cure. Such peroxides include organic peroxides. In many cases it is
preferred to use a
tertiary butyl peroxide having a tertiary carbon atom attached to peroxy
oxygen.
[0048] Exemplary peroxides include: 2,5-dimethy1-2,5-di(t-butylperoxy)hexane;
dicumyl
peroxide; di(2-t-butylperoxyisopropyl)benzene; dialkyl peroxide; bis (dialkyl
peroxide);
2,5-dimethy1-2,5-di(tertiarybutylperoxy)3-hexyne; dibenzoyl peroxide; 2,4-
dichlorobenzoyl peroxide; tertiarybutyl perbenzoate; a,a'-bis(t-butylperoxy-
diisopropylbenzene); t-butyl peroxy isopropylcarbonate, t-butyl peroxy 2-
ethylhexyl
carbonate, t-amyl peroxy 2-ethylhexyl carbonate, t-hexylperoxy isopropyl
carbonate,
di[1,3-dimethy1-3-(t-butylperoxy)butyl] carbonate, carbonoperoxoic acid,
0,0'4,3-
propanediyl 00,00'-bis(1,1-dimethylethyl) ester, and combinations thereof
[0049] The amount of free radical source used generally will be at least 0.1,
0.2, 0.4, 0.6,
0.8, 1, 1.2, or even 1.5; at most 2, 2.25, 2.5, 2.75, 3, 3.5, 4, 4.5, 5, or
even 5.5 parts by
weight per 100 parts of the amorphous fluoropolymer.
[0050] A typical coagent is a compound that comprises a terminal unsaturation
site, which
is incorporated into the polymer during curing to assist with curing,
typically peroxide
curing. Exemplary coagents include: tri(methyl)allylisocyanurate (TMAIC),
triallyl
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isocyanurate (TAIC), tri(methyl)ally1 cyanurate, poly-triallyl isocyanurate
(poly-TAIC),
triallyl cyanurate (TAC), xylylene-bis(dially1 isocyanurate) (XBD), N,N'-m-
phenylene
bismaleimide, diallyl phthalate, tris(diallylamine)-s-triazine, triallyl
phosphite, 1,2-
polybutadiene, ethyleneglycol diacrylate, diethyleneglycol diacrylate, and
combinations
thereof. Another useful coagent may be represented by the formula CH2=CH-Rn-
CH=CH2
wherein Rfl may be a perfluoroalkylene of 1 to 8 carbon atoms. By using the
curing agent
disclosed herein, the amorphous fluoropolymers of the present disclosure can
be cured
without the use of these coagents or can be cured using these coagents,
without the need of
a bromine, iodine, or nitrile end group. In other words, the curable
composition is
substantially free (less than 1, 0.5, or even 0.1 wt % or even below
detection) of a typical
coagent. This can be advantageous because of the coagents expense,
incompatibility with
fluorinated polymers, and impact on processing (e.g., bleeding out of
compositions, mold
fouling).
[0051] The curable composition can also contain a wide variety of additives of
the type
normally used in the preparation of elastomeric compositions, such as
pigments, fillers
(such as carbon black), pore-forming agents, and those known in the art.
[0052] The curable amorphous fluoropolymer compositions may be prepared by
mixing
the amorphous fluoropolymer, the curing agent, along with the other components
(e.g., the
acid acceptor, the onium compound, peroxide, and/or additional additives) in
conventional
rubber processing equipment to provide a solid mixture, i.e. a solid polymer
containing the
additional ingredients, also referred to in the art as a "compound". This
process of mixing
the ingredients to produce such a solid polymer composition containing other
ingredients
is typically called "compounding". Such equipment includes rubber mills,
internal mixers,
such as Banbury mixers, and mixing extruders. The temperature of the mixture
during
mixing typically will not rise above about 120 C. During mixing the components
and
additives are distributed uniformly throughout the resulting fluorinated
polymer
"compound" or polymer sheets. The "compound" can then be extruded or pressed
in a
mold, e.g., a cavity or a transfer mold and subsequently be oven-cured. In an
alternative
embodiment curing can be done in an autoclave.
[0053] Curing is typically achieved by heat-treating the curable amorphous
fluoropolymer
composition. The heat-treatment is carried out at an effective temperature and
effective
time to create a cured fluoroelastomer. Optimum conditions can be tested by
examining
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the cured fluoroelastomer for its mechanical and physical properties.
Typically, curing is
carried out at temperatures greater than 120 C or greater than 150 C. Typical
curing
conditions include curing at temperatures between 160 C and 210 C or between
160 C
and 190 C. Typical curing periods include from 3 to 90 minutes. Curing is
preferably
carried out under pressure. For example pressures from 10 to 100 bar may be
applied. A
post curing cycle may be applied to ensure the curing process is fully
completed. Post
curing may be carried out at a temperature between 170 C and 250 C for a
period of 1 to
24 hours.
[0054] The partially fluorinated amorphous fluoropolymer in the curable
composition has
a Mooney viscosity in accordance with ASTM D1646-06 TYPE A by a MV 2000
instrument (available from Alpha Technologies, Ohio, USA) using large rotor
(ML 1+10)
at 121 C. Upon curing, using the curing agent disclosed herein, the amorphous
fluoropolymer becomes an elastomer, becoming a non-flowing fluoropolymer, and
having
an infinite viscosity (and therefore no measurable Mooney viscosity).
[0055] In one embodiment of the present disclosure, the cure system comprising
the
curing agent and amorphous fluoropolymer disclosed herein, may exhibit both
the
chemical resistance of a typical iodine/bromine and coagent containing
peroxide cure
system, while at the same time elevating the poor heat resistance of these
conventional
iodine or bromine containing fluoroelastomers, due to their lack of bromine or
iodine and
therefore resulting in a cured fluoropolymer having simultaneously sufficient
heat and
chemical resistance.
[0056] The cured fluoroelastomers are particularly useful as seals, gaskets,
and molded
parts in automotive, chemical processing, semiconductor, aerospace, and
petroleum
industry applications, among others.
[0057] Exemplary embodiments include the following:
[0058] Embodiment 1. A curable partially fluorinated polymer composition
comprising:
(i) a partially fluorinated amorphous fluoropolymer, wherein the partially
fluorinated amorphous fluoropolymer comprises carbon-carbon double bonds or is
capable
of forming carbon-carbon double bonds along the partially fluorinated
amorphous
fluoropolymer, wherein the partially fluorinated amorphous fluoropolymer is
substantially
free of bromine, iodine, and nitrile; and
(ii) a curing agent comprising a terminal olefin with at least one olefinic
hydrogen;
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[0059] Embodiment 2. The curable partially fluorinated polymer composition of
embodiment 1 further comprising a peroxide.
[0060] Embodiment 3. The curable partially fluorinated polymer composition of
any one
of the previous embodiments, wherein the curing agent comprises a phenolic
group.
[0061] Embodiment 4. The curable partially fluorinated polymer composition of
any one
of embodiments 1-2, wherein the curing agent comprises a non-aromatic olefinic
alcohol.
[0062] Embodiment 5. The curable partially fluorinated polymer composition of
any one
of the previous embodiments, wherein the curing agent is selected from at
least one of a
di-vinyl and a di-allyl compound.
[0063] Embodiment 6. The curable partially fluorinated polymer composition of
any one
of the previous embodiments, wherein the curing agent is of the formula
CX1X2=CX3-R
wherein Xi, X2, and X3 are independently selected from H, Cl, and F and at
least one of Xi,
X2, and X3 is H; R is a monovalent group comprising a terminal group selected
from an
alcohol, an amine, a thiol, a carboxylic acid, and an olefin.
[0064] Embodiment 7. The curable partially fluorinated polymer composition of
any one
of the previous embodiments, wherein the curing agent is selected from at
least one of:
, 0 ,
H I
H
ij
) ___________________________________________
CF3 __ tOH
0 ___________________________________
0
\\OH
F2
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,H
H
CF3 H
1
H i=
= 'A \" /71
) .............................................................
............................................. /
and combinations thereof, wherein n is an integer from 1 to 10.
[0065] Embodiment 8. The curable partially fluorinated polymer composition of
any one
of the previous embodiments, wherein the partially fluorinated amorphous
fluoropolymer
comprises carbon-carbon double bonds along the backbone of the partially
fluorinated
amorphous fluoropolymer or is capable of forming carbon-carbon double bonds
along the
backbone of the partially fluorinated amorphous fluoropolymer.
[0066] Embodiment 9. The curable partially fluorinated polymer composition of
any one
of the previous embodiments, wherein the partially fluorinated amorphous
fluoropolymer
comprises (i) adjacent copolymerized units of VDF and iFIFP; (ii)
copolymerized units of
VDF and a fluorinated comonomer having an acidic hydrogen atom; (iii)
copolyinerized
units of TFE and a fluorinated comonomer having an acidic hydrogen atom; and
(iv)
combinations thereof.
[0067] Embodiment 10. The curable partially fluorinated polymer composition of
embodiment 8, wherein the fluorinated comonomer having an acidic hydrogen atom
is
selected from: trifluoroethylene; vinyl fluoride; 3,3,3-trifluoropropene-1;
pentafluoropropene; and 2,3,3,3-tetrafluoropropene.
[0068] Embodiment 11. The curable partially fluorinated polymer composition of
any one
of the previous embodiments, wherein the partially fluorinated amorphous
fluoropolymer
is derived from (i) vinylidene fluoride, tetrafluoroethylene, and propylene;
(ii) vinylidene
fluoride, tetrafluoroethylene, ethylene, and perfluoroalkyl vinyl ether, such
as
perfluorNimethyl vinyl ether); (iii) vinylidene fluoride with
hexafluoropropylene; (iv)
hexafluoropropylene, tetrafluoroethylene, and vinylidene fluoride; (v)
hexafluoropropylene and vinylidene fluoride, (vi) vinylidene fluoride and
perfluoroalkyl
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vinyl ether; (vii) vinylidene fluoride, tetrafluoroethylene, and
perfluoroalkyl vinyl ether,
(viii) vinylidene fluoride, perfluoroalkyl vinyl ether,
hydropentafluoroethylene and
optionally, tetrafluoroethylene; (ix) tetrafitioroethylene, propylene, and
3,3,3-
trifluoropropene (x) tetrafluoroethylene, and propylene; (xi) ethylene,
tetrafluoroethylene,
and perfluoroalkyl vinyl ether, and optionally373,3-triftuoropropy1ene; (xii)
vinylidene
fluoride, tetrafluoroethylene, and perfluoroalkyl allyl ether, (xiii)
vinylidene fluoride, and
perfluoroalkyl allyl ether; (xiv) vinylidene fluoride, tetrafluoroethylene,
and
perfluoroalkyloxyallyl ether, (xv) vinylidene fluoride and
perfluoroalkyloxyallyl ether;
(xvi) vinylidene fluoride, tetrafluoroethylene, and perfluoroalkyloxyallyl
ether, (xv)
vinylidene fluoride and perfluoroalkyloxyallyl ether; and (xvi) combinations
thereof
[0069] Embodiment 12. The curable partially fluorinated polymer composition of
any one
of the previous embodiments, wherein the curable composition is substantially
free of a
coagent.
[0070] Embodiment 13. The curable partially fluorinated polymer composition of
any one
of the previous embodiments, further comprising an organo onium compound.
[0071] Embodiment 14. The curable partially fluorinated polymer composition of
embodiment 13, wherein the organo onium compound is selected from at least one
of a
phosphonium or a sulfonium.
[0072] Embodiment 15. The curable partially fluorinated polymer composition of
any one
of the previous embodiments, further comprising an acid acceptor.
[0073] Embodiment 16. The curable partially fluorinated polymer composition of
embodiment 15, wherein the acid acceptor is selected from at least one of
magnesium
oxide, lead oxide, calcium oxide, calcium hydroxide, dibasic lead phosphate,
zinc oxide,
barium carbonate, strontium hydroxide, calcium carbonate, and hydrotalcite.
[0074] Embodiment 17. The curable partially fluorinated polymer composition of
any one
of embodiments 2-16, wherein the peroxide is selected from at least one of 2,5-
dimethy1-
2,5-di(t-butylperoxy)-hexane, dicumyl peroxide, di(2-t-
butylperoxyisopropyl)benzene, and
combinations thereof.
[0075] Embodiment 18. The curable partially fluorinated polymer composition of
any one
of the previous embodiments, comprising 1 to 10 millimoles of the curing agent
per 100
parts of the partially fluorinated amorphous fluoropolymer.
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[0076] Embodiment 19. An article comprising the cured composition of any one
of
embodiments 1-18.
[0077] Embodiment 20. The method of making a partially fluorinated elastomer
comprising:
providing the curable partially fluorinated polymer composition of any one of
embodiments 1- 18; and
curing the curable partially fluorinated polymer composition.
EXAMPLES
[0078] Advantages and embodiments of this disclosure are further illustrated
by the
following examples, but the particular materials and amounts thereof recited
in these
examples, as well as other conditions and details, should not be construed to
unduly limit
this invention. In these examples, all percentages, proportions and ratios are
by weight
unless otherwise indicated.
[0079] All materials are commercially available, for example from Sigma-
Aldrich
Chemical Company; Milwaukee, WI, or known to those skilled in the art unless
otherwise
stated or apparent.
[0080] These abbreviations are used in the following examples: phr = parts per
hundred rubber; g
= grams, kg = kilograms; min = minutes; mol = mole; hr = hour, C = degrees
Celsius;, mL =
milliliter; L = liter; mm= millimeter; kN= Kilo-Newtons; kPa = Kilo-Pascals;
GC/MS = gas
chromatography mass spectrometry; Pa = Pascal; psig = pounds per square inch;
LC/UV= liquid
chromatography ultraviolet detection; and phr = per hundred parts rubber (or
amorphous polymer).
Materials
Name Description
TFE Tetrafluoroethylene
VDF Vinylidenefluoride
HFP Hexafluoropropylene
Propylene
BTFE Bromotrifluorethylene
VDF/HFP A VDF/HFP copolymer commercially available from
3M Co.
St.Paul, MN under the trade designation "3M Dyneon Ultra High
Viscosity Fluoroelastomer FC-2299"
VDF/BTFE/MA31 Amorphous copolymer of VDF/BTFE and
CF2=CFCF20C3F60CF3(MA31) made according to "Preparation
of VDF/BTFE/MV31"
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Name Description
VDF/TFE/P #1 Base resistant amorphous fluoropolymer 35 mole %
VDF/40
mole % TFE/ 25 mole % P made according to "Preparation
VDF/TFE/P#1"
VDF/TFE/P #2 Amorphous copolymer of VDF/TFE/P commercially
available
from Asahi Glass, Tokyo, Japan under the trade designation
AFLAS 200P.
VDF/TFE/HFP Amorphous copolymer VDF/TFE/HFP terpolymer made
according to "Preparation VDF/TFE/HFP"
Carbon black N990 carbon black commercially available from
Cabot, Boston,
MA
Silica filler Commercially available from US Silica, Frederick,
MA under the
trade designation "MIN-U-SIL 5"
Onium 1 Triphenylbenzylphosphonium chloride
cure accelerator
commercially available from Sigma-Aldrich, St.Louis, MO
Onium 2 Organophosphonium cure accelearator commercially
available
from 3M, St.Paul, MN under the trade designation "Dynamar FX
5166".
Eugenol Terminal olefin, 4-ally1-2-methoxyphenol
commercially available
from Sigma-Aldrich, St.Louis, MO
CH2=CHCH2- Terminal olefin, prepared as per "Curative ally'
ether of
OCH2C4F8CH2-0H octafluorohexane diol (CH2=CHCH2- OCH2C4F8CH2-0H)"
(OFHDAE)
BF6DAE Terminal olefin, prepared as per "Curative Diallyl
Ether of
Bisphenol AF (BF6DAE)"
BF6MAE Terminal olefin, prepared as per "Curative
Monoallyl Ether of
Bisphenol AF (BF6MAE)"
4-hydroxybenzophenone Onium stabilizer commercially available from Sigma-
Aldrich,
St.Louis, MO
Peroxide Peroxide commercially available under the trade
designation
"VAROX DBPH-50" from R.T. Vanderbilt Company, Inc.,
Norwalk, CT
Hydrotalcite An acid acceptor. Layered double hydroxide of
general formula
Mg6Al2CO3(OH)16 4 (H20), commercially available from
Kyowa Chemical, Tokyo, JP under the trade designation "DHT-
4A"
MgO An acid acceptor. Magnesium oxide powder
commercially
available from Akrochem Corp., Akron, Ohio under the trade
designation "ELASTOMAG 170"
Ca(OH)2 An acid acceptor. Calcium hydroxide commercially
available under the trade designation "Rhenofit CF" from
RheinChemie, Mannheim, Germany
[0081] Preparation of VDPBTFENIA31
[0082] Under oxygen-free condition a 4 liter kettle was charged with 3400 mL
deionized water.
12g CF3-0-(CF2)3-0-CFH-CF2-COONH4 was added as emulsifier. After heating to 90
C 40g
tetrafluoroethene (TFE), 77g VDF, 3g 1-bromotrifluoroethene (BTFE) were added
and 140g
perfluoro-4,8-dioxa-1-nonene (MA31, prepared analogously to "PMEAE" in U.S.
Pat. No.
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5,891,965 Worm et al.) was added as preemulsion (described in W0200149752).
The reaction was
initiated with addition of 1,4g ammonium peroxodisulphate (APS) dissolved in
280mL deionized
water by continuously feeding. At 10 bar pressure and 90 C 200g TFE, 380g
VDF, 6.2g BTFE,
560g MA31 (as preemulsion) were fed over a period of 190 min. The resulting
latex had a solid
content of 27% and was coagulated with 12g MgC12. The resulting 1.1kg polymer
was dried at 130
C.
[0083] The composition of the resulted polymer was 13.5 mole % MV31, 69.7
mole% VDF,
16.1mole% TFE, and 0.7mole% BTFE. The glass transition temperature (by DSC)
was Tg=-42 C
and Mooney-Viscosity (1+10', 121 C) was 51.
[0084] Curative Diallyl Ether of Bisphenol AF (BF6DAE)
[0085] In a 3-neck 1 liter round bottom flask equipped with a mechanical
stirrer,
condenser and a thermocouple was charged with 100g, 0.3mol of HO-
C6H4C(CF3)2C6H4-
OH, 117g, 0.97mo1 ally! bromide, 12g, 0.04mol tetrabutyl ammonium bromide that
was
dissolved in 4g deionized (DI) water and 250g glyme. The solution was stirred
and heated
to 50 C. A solution of 53g, 0.94mo1 KOH dissolved in 34g DI water was added
drop wise
over 30 min resulting in a precipitate and a temperature increase to 62 C. The
reaction
was heated to 65 C for two hrs before cooling to 25 C. The top glyme solution
phase was
removed and placed in a round bottom flask and had glyme removed by atmosphere
distillation. The viscous product was dissolved in 100g methyl tert-butyl
ether and
placed on a glass tray evaporated the solvent and then heated for 20 hours at
60 C/1.6 kPa
(12torr) in a vacuum oven to isolate 124g viscous product for a quantitative
yield. LC/UV
analysis gave mole percent of the following: 91.6% CH2=CHCH2-0C6H4C(CF3)2C6H40-
CH2CH=CH2 and 1.4% CH2=CHCH20C6H4C(CF3)2C6H4-0H. The material as
synthesized was diluted in methanol to a 50% solids concentration in order to
better
facilitate the incorporation into the polymer.
[0086] Curative Monoallyl Ether of Bisphenol AF (BF6MAE)
[0087] In a 3-neck 2 liter round bottom flask equipped with a mechanical
stirrer,
condenser and a thermocouple was charged with 250g, 0.7mol of HO-
C6H4C(CF3)2C6H4-
OH, 30g, 0.3mol ally! bromide, 5g, 0.02mol tetrabutyl ammonium bromide that
was
dissolved in 4g DI water and 500g glyme. The solution was stirred and heated
to 50 C. A
solution of 16g, 0.3mol KOH dissolved in 18g DI water was added drop wise over
15 min
resulting in a precipitate and a temperature increase to 62 C. The reaction
was heated to
65 C for one hr before cooling to 25 C. The top glyme solution phase was
removed and
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placed in a round bottom flask and rotary evaporated at 50 C/2 ton. This was
followed by
heating to 50 C at 0.13 kPa (1 ton) using a vacuum pump for one hour followed
by the
addition of 400g of chloroform and stirred slurry for 20 hrs. The slurry was
filtered and
the solution was rotary evaporated at 50 C/20 torr isolated 50g viscous oily
product. A
second chloroform extraction done to the solids gave 21g of additional oily
product for a
76% yield. LC/UV analysis gave mole percent of the following: 66.8% CH2=CHCH2-
0C6H4C(CF3)2C6H4-0H, 6.6% CH2=CHCH20C6H4C(CF3)2C6H40-CH2CH=CH2, and
23.7% of HO-C6H4C(CF3)2C6H4-0H. The isolation of allyl ether phenyl
hexafluorofluoroisopropylidene phenol was done by flash chromatography
(available
under the trade designation "INTELLIFLASH 280", Analogix Co., Santa Clara, CA)
with
a silica gel column eluding first with heptane as the nonpolar solvent and
ending with
ethyl acetate as the polar solvent. LC/UV analysis gave 99.23 mole percent of
CH2=CHCH2-0C6H4C(CF3)2C6H4-0H. The material as synthesized was diluted in
methanol to a 50% solids concentration in order to better facilitate the
incorporation into
the polymer.
[0088] Curative Allyl Ether of Octafluorohexane Diol (OFHDAE /CH2=CHCH2-
OCH2C4F8CH2-0H)
[0089] In a 3-neck 500 ml round bottom flask equipped with a mechanical
stirrer,
condenser and a thermocouple was charged with 50g, 0.19mol of HO-CH2C4F8CH2-0H
available from Exfluor Research Corporation and 150g of methyl-t-butyl ether.
The
solution was stirred and added a solution of 12g, 0.18mol KOH dissolved in 26g
DI water
followed by 2g, 0.01mol tetrabutyl ammonium bromide that was dissolved in 3g
DI water.
The solution was stirred and heated to 50 C and 22g, 0.18mol allyl bromide was
added
drop wise over 20 min and kept at 50 C for two hrs before cooling to 25 C.
[0090] The top methyl-t-butyl ether solution phase was removed and placed in a
round
bottom flask and evaporated at 50 C/1.33 kPa (10 ton), using a rotary
evaporator. A
charge of 55g of hexane to the product mixture and stirred to give two phases.
The bottom
phase was extracted with an additional 50g of hexane. The bottom phase was
washed
twice with chloroform to extract the desired product and filtered to remove
insoluble
starting diol. The chloroform solution was removed and placed in a round
bottom flask
and evaporated at 55 C/10torr using a rotary evaporator to isolate 19g product
mixture.
GC/MS analysis gave mole percent of the following: 84% CH2=CHCH2- OCH2C4F8CH2-
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OH, 12.5% CH2=CHCH2- OCH2C4F8CH2O-CH2CH=CH2 and 3.9% HO-CH2C4F8CH2-
OH. The material as synthesized was diluted in methanol to a 50% solids
concentration in
order to better facilitate the incorporation into the polymer.
[0091] Preparation VDF/TFE/HFP
[0092] In a 2000 gallon (7570 L) kettle was charged 13,180 pounds (5978 kg) of
DI water, 50
pounds (22.6 kg) of a 50% solution of potassium hydrogen phosphate in water, 2
pounds (0.9 kg)
of hexamethyldisilane, and then the solution was heated to 160 F. Agitation
was set at 100 rpm.
The kettle was pressurized with 155 pounds (70 kg) of HFP, 38 pounds (17 kg)
of VDF and 53
pounds (24 kg) of TFE to a pressure of 130 psig (896 kPa). The polymerization
was initiated with
12 pounds (5 kg) of ammonium persulfate. As the reaction started the pressure
was maintained at
130 psig (896 kPA) by adding VDF/TFE/HFP at a ratio of 1/0.739/1.330. The
reaction temperature
of 160 F (71 C) was maintained. When 1726 pounds (783 kg) of VDF was added
the HFP valve
was closed and an additional amount of VDF and TFE was added at a ratio of
VDF/TFE = 1.4/1
until 70 pounds (32 kg) of VDF was added. The latex was free of coagulum and
had a solids
content of approximately 28%. The polymer was isolated by coagulation with
magnesium
chloride, washed with DI water, and oven dried at 266 F (130 C) for until a
moisture content of <
0.5 weight % was reached.
[0093] Preparation VDF/TFE/P#1
[0094] In a 2000 gallon (7570 L) kettle was charged 12,940 pounds (5869 kg) of
DI water and 50
pounds (23 kg) of a 50% solution of potassium hydrogen phosphate in water, the
solution was then
heated to 160 F (71 C). Agitation was set at 100 rpm. The kettle was
pressurized with 189 pounds
(86 kg) of VDF and 111 pounds (50 kg) of TFE to a pressure of 220 psig (1516
kPa). Then the
polymerization was initiated with 60 pounds (27 kg) of ammonium persulfate. As
the reaction
started the pressure was maintained at 220 psig by adding VDF/TFE/propylene at
a ratio of
1/1.885/0.394. The reaction temperature of 160 F (71 C) was maintained. When
1487 pounds
(674 kg) of VDF was added the VDF valve was closed and an additional amount of
TFE and
propylene was added at a ratio of TFE/P = 4:1 until 40 pounds (18 kg) of TFE
was added. The
latex was free of coagulum and had a solids content of approximately 27%. The
polymer was
isolated by coagulation with magnesium chloride, washing with DI water, and
drying at 280 F
(138 C) until a moisture content of < 0.5 weight per cent was reached.
[0095] Methods
[0096] HARDNESS:
[0097] Hardness Shore A (2") was measured on post cured samples according to
ASTM
D-2240 (2010) and as indicated in Table 2 and 3.
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[0098] TENSILE STRENGTH AND ELONGATION:
[0099] Tensile strength and elongation were determined on post cured samples
using a
mechanical tensile tester (Instron, Norwood, MA) with a 1 kN load cell in
accordance with
DIN 53504 (2009) (S2 DIE) at a constant cross head displacement rate of 200
mm/min as
indicated in Table 2 and 3.
[00100] CURE RHEOLOGY
[00101] Cure rheology tests were carried out using uncured,
compounded samples
using a rheometer marketed under the trade designation Monsanto Moving Die
Rheometer
(MDR) Model 2000 by Monsanto Company, Saint Louis, Missouri, in accordance
with
ASTM D 5289-93a at 177 C, no pre-heat, 30 min elapsed time, and a 0.5 degree
arc. Both
the minimum torque (ML) and highest torque attained during a specified period
of time
when no plateau or maximum torque (Mu) was obtained were measured. Also
measured
were the time for the torque to increase 2 units above ML (t52), the time for
the torque to
reach a value equal to ML + 0.5(MH - ML), (t'50), and the time for the torque
to reach ML +
0.9(MH - ML), (t'90) as well as the tan(delta) at ML and Mu. Tan(delta) is
equal to the
ratio of the tensile loss modulus to the tensile storage modulus (lower
tan(delta) means
more elastic).0-RING MOLDING AND COMPRESSION SET
[00102] 0-rings having a cross-section thickness of 0.139 inch (3.5
mm) were
molded (15 min cure at 177 C) followed by a postcure in air for 16 hrs at 232
C. The 0-
rings were subjected to compression set testing following a similar method as
described in
ASTM 395-89 method B (analyzed in triplicate), with 25 % initial deflection at
variable
time and temperature as per Tables 2 and 3.
[00103] For each of the Examples (E) and Comparative Examples (CE),
the
amounts of the components used (with the amount per 100 parts of rubber listed
in
parenthesis) as shown in Table 1 were compounded on a two-roll mill. Cure
Rheology
evaluations were carried out for each Example and Comparative Example using
the test
method described above. The results are shown in Table 2 and 3. 0-rings were
molded,
cured (press cured for 15 min at 177 C and postcured for 16 hrs at 232 C)
and evaluated using
the method "0-Ring Molding and Compression Set" as described above. The
results are
shown in Table 4.
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TABLE 1
Sample Rubber Terminal Onium Acid
Peroxide Carbon
olefin Acceptor black
El VDF/HFP Eugenol Oniuml Ca(OH)2 (6) 2.5
30
(100) (2) (1) MgO (3)
E2 VDF/HFP Eugenol
Onium2 hydrotalcite 2.5 30
(100) (2) (1.5) (6)
E3 VDF/HFP OFHDAE Onium2 Ca(OH)2
(6) 2.5 30
(100) (4.4) (3) MgO (3)
E4** VDF/HFP BF6DAE Onium2 Ca(OH)2
(6) 2.5 30
(100) (4.4) (1.5) MgO (3)
E5 VDF/HFP BF6MAE Oniuml Ca(OH)2
(6) NONE 30
(100) (4.3) (1) MgO (3)
E6 VDF/HFP BF6MAE Oniuml Ca(OH)2
(6) 2.5 30
(100) (4.3) (1) MgO (3)
E7 VDF/HFP Eugenol Onium2 Ca(OH)2 (6)
NONE Silica
(100) (2) (1.5) MgO (3)
filler
instead
(30)
E8 VDF/TFE/P Eugenol Onium2 Ca(OH)2 (6)
2.5 30
#1(100) (2) (3) MgO (3)
E9 VDF/TFE/P Eugenol Onium2 Ca(OH)2 (6)
2.5 30
#2(100) (2) (1.5)
E 1 0* VDF/TFE/P Eugenol NONE Ca(OH)2 (6) 2.5
30
#2(100) (2) added*
CEA VDF/TFE/P Eugenol NONE NONE 2.5 30
#2(100) (2) added*
Ell VDF/BTFE/ Eugenol Onium2 Ca(OH)2 (6)
2.5 30
MA31 (100) (2) (1.5) MgO (3)
* = 1H-NMR analysis shows that VDF/TFE/P #2 (AFLAS 200P) contains an onium.
The
combined 1D and 2D 1H-NMR spectral data were used to positively confirm the
presence of a
small amount of a component with a tetrabutylammonium cationic specie (0.36
wt.% of
(CH3CH2CH2CH2)4-N(+).
** = also contains 2 phr 4-hydroxybenzophenone
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TABLE 2
El E2 E3 E4 E5 E6 E7 E8
ML, in-lb(N-m) 4.37 4.32 5.4 2.94 3.46 4.09
5.52 1.13
MH, in-lb(N-m) 18.9 7.85 20.1 7.44 8.48 16.0
12.1 11.8
Delta torque 14.5 3.53 14.7 4.5 5.02 11.9
6.6 10.7
t52, min 0.69 0.65 0.4 0.48 0.49 0.43
0.51 1.49
t'50, min 1.61 0.58 1.24 0.54 0.51 0.89
0.73 3.13
t'90, min 5.54 3.25 4.98 6.86 1.97 5.74
3.33 8.05
Tan(delta) @ MH 0.046 0.118 0.047 0.152 0.168 0.048 0.104 0.100
NT= not tested
TABLE 3
E9 El0 CEA Ell
ML, in-lb(N-m) 1.4 1.48 1.3 1.75
MH, in-lb(N-m) 17.96 10.37 1.97 14.08
Delta torque 16.56 8.89 0.67 12.33
t52, min 1.02 2.63 n/a 1.5
t'50, min 3.14 4.88 3.16 3.78
t'90, min 8.37 9.87 8.79 8.53
Tan(delta) @ MH 0.037 0.087 0.507 0.064
NT= not tested
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TABLE 4
El E3 E4 E5 E7 E8 E9 Eli
Tensile strength (psi)
2939 2516 2289 2820 1873 2405 2956 1477
Tensile strength (psi)
1911 2463 1901 1872 NT NT NT NT
Heat aged 72 hr 50 C
Tensile strength (psi)
903 NT NT 1009 NT NT NT NT
Steam aged 168 hrs 250 C
Elongation at break (%) 171 71
124 117 132 112 100 64
Elongation at break (%) Heat aged 72 hr
167 61 86 103 NT NT NT NT
250 C
Elongation at break (%) Steam aged 168
28 NT NT 17 NT NT NT NT
hrs
100% modulus (psi)
1451 NT 1741 2335 1505 2064 2956 NT
100% modulus (psi)
1247 NT NT 1224 NT NT NT NT
Heat aged 72 hr 50 C
Hardness (ShoreA) 80 84 85 79 80 81 81
84
Hardness (ShoreA)
82 NT 89 86 NT NT NT NT
Heat aged 72 hr 50 C
Hardness (ShoreA)
90 NT NT 89 NT NT NT NT
Steam aged 168 hrs
Compression set % (72 hrs @ 200 C).
34 63 65 34 37 47 65 59
16 hr postcure 232 C
Compression set % (72 hrs @ 230 C).
59 93 102 83 NT 86 94 NT
16 hr postcure 232 C
NT= not tested
[00104] Foreseeable modifications and alterations of this invention will
be apparent
to those skilled in the art without departing from the scope and spirit of
this invention.
This invention should not be restricted to the embodiments that are set forth
in this
application for illustrative purposes.
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