EPDM, Acrylic and CSM

rubbers
Muhammad Farooq
POLYMER VARIABLES AND
PROPERTIES
• In addition to variations resulting from the introduction of the different
termonomers, several other variations are possible in EPDM's. All of them affect
the resultant properties of the polymers.
(E-P) Ethylene-propylene Composition
• The contents of E-P elastomers are generally reported as weight-percent
ethylene and vary from 75 to 45%. The monomers are randomly distributed,
resulting in amorphous type copolymers. The higher ethylene-containing
polymers, which contain some crystallinity, are beneficial in that they possess
higher green strength (shape retention), can be more highly loaded with
fillers/oil, result in higher compounded tensile strengths, can be more readily
pelletized, and possess better extrusion properties.
• The disadvantages of the higher ethylene contents, however, are their poorer
mill processing behavior at lower temperatures, inferior low-temperature
properties, and their difficulty in being mixed. It is appropriate to store high
ethylene terpolymers under sufficient warmth to minimize dispersion problems.
Molecular Weight
• The molecular weight of an elastomer is commonly reported as the
Mooney viscosity (ML). In the case of EPDM's, these values are obtained
at elevated temperatures, usually 125 °C. The primary reason for this is to
melt out any effect that high ethylene content could produce
(crystallization), thus masking the true molecular weight of the polymer.
• Mooney viscosities can vary from a low of 20 to a high of 100. Polymers
of even higher molecular weight exist but are extended with oil (25 to 100
phr). Such polymers should be stored in the absence of light (UV) since
the oils will tend to accelerate oxidative degradation (gelation).
• Advantages of higher molecular weights are similar to those of higher
ethylene contents in that tensile and green strength improve. In addition,
these polymers can be more highly loaded with fillers and oil.
• Disadvantages are their poorer processing and dispersibility.
Molecular-weight Distribution (MWD)
• Molecular-weight distribution is not normally reported as a polymer variable
but in most applications it is a very important property. A measure of the MWD
is now commonly obtained through the use of Gel Permeation Chromatography
at elevated temperatures ( 135 C).
• This value can usually vary from 2 to 5. For broad MWD polymers, there is
usually a variation in E-P composition as well. The end with the higher
molecular weight possesses a higher ethylene content than the end with the
low molecular weight.
• Polymers with broad molecular weight possess excellent mill processing and
calendering capabilities and higher green strength. These polymers are
extensively used for applications that don't allow large loadings of filler and oil.
• Their disadvantages are their slower cure rate and poorer state of cure. Narrow
molecular weight distributions are more common for EPDM's since they result
in faster cure rates, better state of cure, and smoother extrusions.
Diene Type
Ethylidene Norbornene (ENB)

• ENB is the most widely used termonomer employed even though it is

the most expensive, the reasons being that it is the most readily
incorporated during copolymerization and the double bond introduced
has the greatest activity for sulfur vulcanization.
• This activity is also of such a nature that EPDM's containing ENB have
the greatest tendency to be cocured with diene elastomers. Another
unique characteristic of this termonomer is that it makes it possible to
prepare linear as well as branched polymers by varying the conditions
under which the polymers are synthesized.
• Branching has an important role in establishing the rheological
properties of a polymer. Under proper control, it can introduce
properties to the EPDM that are beneficial in certain applications.
PROCESSING

• Conventional rubber equipment is used for the processing of EPDM

compounds. Selection of the polymer or blend of polymers is an
essential consideration in order to obtain optimum processibility
Mixing
• Mixing usually is accomplished with an internal mixer, such as a
Banbury mixer. In some instances, it may be desirable or necessary to
use the mill mixing process. For mill mixing, the low-viscosity, higher-
propylene EPDM types are preferred. The higher-viscosity and higher-
ethylene polymers are considered too difficult for practical mill
mixing. Furthermore, compounds based on these polymers typically
contain such high amounts of filler and oil that mill mixing is usually
impractical from this standpoint alone.
 continued
• Although all types of EPDM are suitable for the internal mixer, no single
mixing procedure is satisfactory for all compounds. The variety of
polymers, the range of compound qualities (which affect choice of filler
type), and the condition of the particular mixer are some of the factors
that influence the mixing technique.
• The most popular procedure is to load the ingredients in "one shot,"
and often the batch is loaded "upside-down" (rubber put in last, after
fillers, oils, and so forth). Depending upon the particular machine (its
mechanical condition, speed, and so forth) mixing cycles can range from
3 to 7 minutes. Using this kind of procedure, the batch is usually
dumped when the temperature reaches 115°C to 130°C. This procedure
may be limited to compounds that are based on medium- and low-
ethylene polymers loaded with mineral fillers and/or semi-reinforcing
types of carbon black (SRF, GPF, FEF).
 continued
• For compounds utilizing high-ethylene or very-high-molecular-weight
EPDM polymers and for compounds containing reinforcing carbon blacks
(HAF, ISAF), the "one-shot" or "upside-down" loading procedure often
results in poor dispersion of black or rubber or both. These polymers and
blacks will usually not disperse well if processing oil is added early in the
mixing cycle. Better dispersion is attained by an incremental procedure in
which rubber and part of the black are loaded into the mixer with little or
no oil. The withheld black and oil may then be added in one, two. or
more increments.
• If allowable from the standpoint of providing required properties, an
easy to-disperse softer black or higher structure black, should be used in
combination with the more difficult to disperse:, highly reinforcing black.
Then the easy-to-disperse black can be added with the plasticizer as the
second increment in the mixing procedure. As was mentioned previously,
high ethylene EPDM's should be stored under warm warehouse
conditions to minimize dispersion problems.
Extrusion
• The selection of polymer is a prime consideration if the EPDM compound is to
be used for extrusion processing. The high-ethylene types are most useful for
this process because they provide good green strength for shape retention. In
addition, some green strength seems necessary for good feeding into the
extruder; in fact. lack of green strength in the uncured compound is usually
associated with poor feeding characteristics. If compounds do not feed easily,
and if feed is erratic, surging of the extrudate results in its size varying. Hence
a well-designed extrusion compound should contain enough high-ethylene
polymer to provide the desired processing behavior
• Since excessive green strength (tough compound) is a possibility, one of the
lower ethylene types of EPDM should be part of the polymer blend to avoid it.
A wide variety of extrusion equipment is to be found. Most of the older
extruders still in use are the short-barrel, hot-feed type, and for these the
stock must usually be "warmed" on a mill and then fed to the extruder.
continued
• This process, therefore, requires a compound that is reasonably easy to
band on the warm-up mill. Excessive green strength and/or high
compound viscosity will cause difficulty in banding and may also cause
bagging. These results may be avoided by using a lower-ethylene
and/or lower-viscosity polymer blended with the high ethylene type in
the compound. In general, the newer cold feed extruder is preferred.
• Not only does it obviate the need for a warm-up mill, it also provides
better control of processing conditions so that more uniform extrudates
are obtained. For most compounds. the extruder screw should be
operated at a higher temperature than the barrel. Conditions should be
adjusted to provide a smooth surface and optimum rate of extrusion. In
general, extrusion temperature conditions are somewhat higher for
EPDM compounds than for other types of rubber compounds.
Molding
• EPDM compounds have proved to be particularly suitable for injection
molding. When properly compounded, EPDM provides a fast cure rate
and good flow and is not prone to reversion at the high curing
temperatures common to this process.
• Compounding considerations for injection molding are not
appreciably different from those for compression or transfer molding.
• The curing system is usually the point of most concern and the
plasticizer should be selected for low volatility at the processing
temperature.
Calendering
• The EPDM polymer selected for calendering should be in the medium-
to high propylene range.
• If the compound is to be lightly loaded, the lowest-viscosity, highest-
propylene type is most suitable. Also, a polymer with broad molecular
weight distribution and medium- to high-propylene content is a better
choice.
• For medium to highly loaded compounds, the higher-viscosity types
are required.
• The desirable processing is also often attained by a proper selection of
two types of EPDM polymers.
ELEMENTS OF COMPOUNDING EPDM
Curing System for EPDM
• If one substitutes one EPDM for another in an existing formulation
without changing the cure system, the rate of cure and the properties
will almost certainly not be the same, particularly if the two polymers
utilize different third monomers. The properties also can be affected
by differences in molecular weight and other variations in polymer
composition.
• In general, polymers with DCPD or l ,4 HD will require somewhat more
active accelerators and/or higher levels to provide satisfactory cure
rates.
• As already discussed, EPDM has pendant unsaturation that allows
sulfur vulcanization. Like most other synthetic rubbers, common
accelerators may be used
continued
• Usually, however, the cure system will contain a thiazole accelerator
(MBT, MBTS, or the like) in combination with a thiuram and/or a
dithiocarbamate.
• Sulfur donor-type accelerators may replace elemental sulfur, if heat
resistance and/or compression set requirements are severe. For some
molded-goods applications, accelerator bloom may be unacceptable.
• Approximate limits for most commonly used accelerators are as
follows:
Reinforcement
• As is true of other non-crystallizing polymers, EPDM requires
reinforcement to be of practical value since the mechanical properties
of the unfilled rubber are quite poor.
• Carbon black is the most useful material for this reinforcement, but
silica, clay, talc and some other mineral fillers may also be used. To
attain their full effectiveness as reinforcing agents in EPDM rubbers,
carbon black and other fillers must be well dispersed.
• High tensile strength, good tear resistance, and improved abrasion
resistance are usually associated with good reinforcement.
• Well-mixed batches also provide better and more uniform processing
for extrusion, calendering, molding, and so forth.
Plasticizers and Processing Aids
• Naphthenic oils have been the most widely used plasticizers for EPDM
compounds because they provide the best compatibility at reasonable cost. For
applications at higher temperatures or in colored compounds, paraffinic oils are
usually chosen because of their lower volatility and improved UV stability.
• Some paraffinic oils tend to bleed from cured, high-ethylene EPDM compounds.
If such oils must be used, it is usually advisable to replace part (20- 25 phr) of
the high-ethylene rubber with one having somewhat lower ethylene content.
• Aromatic oils have an adverse effect on some compound properties and, of
course, must not be used in conjunction with peroxide curing systems. Stearic
acid, zinc stearate, or other internal lubricants are often included in a
compound to aid processing. EPDM compounds are inherently not tacky.
Should there be a need for building tack, it would be necessary to add a
tackifier to the compound.
Acrylic elastomers
• Acrylic elastomers are copolymers based on two major components:
the backbone (95-99%) and the reactive cure site (1-5%) shown in
Figure below. Reactivity of the cure site monomer governs the cure
behavior of the polymer.
Method of Manufacture
• Conventional acrylic elastomers are commonly emulsion-polymerized to form
a latex, or are polymerized in suspension. The solid product is recovered by
conventional coagulation, washing procedures, and dried by hot air, vacuum,
or extrusion techniques. The ethylene/acrylic type is solution-polymerized
under pressure. However, its method of recovery is not revealed in the
literature.
Raw Polymer Characteristics
• Conventional acrylic polymers have a specific gravity of 1.10 and are off-white
in color. Current commercial types are manufactured in a 25-55 Mooney (ML
1 + 4 100°C) viscosity range. All are normally supplied in solid, slab form.
Some special solution grades are also available in both solid and crumb form.
The ethylene/acrylic polymer has a specific gravity of 1.03, is pale-gray in
color, and supplied in a 16 ± 3 Mooney (ML 1 + 4 100°C) viscosity range.
Physical Characteristics
• As a class, acrylic elastomers are inherently resistant to:
1. Temperatures from -40 to 204C (400°F)
2. Oils at elevated temperatures.
3. Oxidation.
4. Ozone.
5. Aliphatic hydrocarbons.
6. Sunlight (UV) discoloration.
• Typical vulcanizate properties are as follows:
• Tensile Strength (MPa/psi) 5-17/700-2500
• Elongation (%) 100-600
• Hardness (Duro A) 40-90
 continued
• In addition, the acrylics exhibit good damping qualities, are not highly
corrosive to steel, and can be compounded to provide excellent flex life,
fair electrical insulation resistance and some degree of flame resistance.
The more polar conventional acrylics can also be compounded to
provide a high degree of electrical conductivity. The ethylene/acrylic
type also provides improved abrasion resistance, but tends to lose this
advantage after oil-aging as a result of its high swell characteristics.
• Ethyl-acrylate-base polymers provide the best overall balance of
processing characteristics, physical properties, and heat and oil
resistance, but possess limited low-temperature resistance. The newer,
improved low-temperature versions exhibit some sacrifice in this
balance. The choice of polymer is primarily dependent on the balance
of low-temperature/oil-swell resistance required for a given application
Heat, Fluid, Low-temperature Resistance
• The high-temperature service capability of acrylic elastomers is rated at > 70 hr
maximum/190-204°C short term, intermittent; and > 1000 hr maximum/ 163-
177°C long term, continuous, in dry heat. Short-term exposure above 204 is also
possible. The ultimate mode of heat-aging failure for all acrylic elastomers is
embrittlement.
• Acrylic elastomers are highly resistant to petroleum base lubricating oils,
transmission fluids and greases, including the sulfur-bearing, extreme-pressure
gear lubricants. In addition, they are also quite resistant to the newer, longer
service SF and synthetic ester-type lubricants. The use of butyl acrylate and
ethylene/acrylic-based polymers is limited to applications that can tolerate high
oil-swell characteristics. Acrylic elastomers are not recommended for service in
aromatic hydrocarbons, e.g., gasoline. Most conventional acrylic polymers are
also not suitable for continuous use in hot water or steam, or in water soluble
materials such as methanol or ethylene glycol. However, the ethylene/ acrylic
type is recommended for service in hot water and in ethylene glycol media.
General Compounding
Cure Systems
• Because acrylic elastomers have a saturated backbone, crosslinking is accomplished
via incorporation of copolymerized reactive cure sites. The nature of this cure site
varies in commercial products, and therefore different cure systems have been
developed for specific types. Thus acrylic elastomers from different suppliers are not
generally directly interchangeable in a given recipe.
• Conventional domestic acrylics respond to soap/amine, activated thiol, soap/sulfur
or sulfur donor, lead/thiourea, diamine and trithiocyanuric acid {TCY) cure systems.
The ethylene/acrylic type responds to diamine and peroxide cures.
• Since the majority of acrylic cure systems are basic in nature, they are retarded by
acids and accelerated by bases. Specific cure-system recommendations should be
obtained directly from the polymer suppliers. Despite significant advancements in
acrylic-cure technology, all current, state of-the-art acrylic elastomers require a
relatively long cure cycle or must be subsequently post-cured (tempered) in a
circulating hot-air environment to realize optimum compression-set resistance
General Processing
Mixing
• Acrylic compounds can be Banbury- or mill-mixed. However, internal
Banbury mixing is preferred and generally utilized by the industry. A
two-pass Banbury-mix procedure is most common, but a one-pass
mix is also possible on relatively non-scorchy compounds.
• An "upside-down" mixing procedure is sometimes desirable for use
with highly loaded, dry compounds.
• Because acrylic elastomers are somewhat thermoplastic in nature and
tend to lose shear resistance fairly rapidly on mixing, it is
recommended that reinforcing agents be incorporated very early in
the mixing cycle to obtain good dispersion.
Vulcanization
• Acrylic elastomers lend themselves to all common cure processes. They
are commonly compression-, transfer- and injection-molded, but can be
steam-cured as well. Typical cure cycles (in minutes) are as follows:

• In addition, acrylic elastomers respond to most continuous vulcanization

(CV) cure techniques. Special compounding may be required for the low
viscosity types to gain adequate backpressure in compression molding
operations. As indicated previously, a post-cure is usually necessary to
develop optimum compression-set resistance. Oven post-cure cycles in
the range of 4-8 hr/17C are commonly utilized. More comprehensive
processing recommendations are available from the polymer suppliers.
Chlorosulfonated Polyethylene
• Chlorosulfonated polyethylene is not made from component
monomers but from the chemical modification of polyethylene. The
chlorination and chlorosulfonation of polyethylene are carried out
simultaneously or sequentially using carbon tetrachloride as the
reaction solvent.
• The elastomeric character of CSM arises from the inherent flexibility
of the polyethylene chain due to reduced crystallinity. Substitution of
chlorine in the polymer chain provides sufficient molecular
irregularity to reduce crystallinity. The sulfonyl chloride groups
provide cross-linking sites for non-peroxide vulcanization. CSM
properties can vary from elastomeric to plastic depending on the
amount of chlorine and sulfonyl chloride substitution.
continued
• The presence of sulfonyl chloride groups contributes to adhesion and mechanical
reinforcement by reaction with fillers. In addition, the presence of chlorine imparts
significant flame and light resistance to CSM compounds. However, all of these
properties depend on the extent and distribution of the chlorination and
cholrosulfonation. CSM polymers can be easily functionalized by replacement of
the halogen either on the backbone or on the sulfonyl group. Acid, ester, and
amide derivatives of the sulfonyl chloride groups have been prepared. The sulfonyl
chloride group is the cure site for CSM and determines the rate and state of cure.
Carbon black fillers give the best reinforcement as well as significant resistance to
photochemical degradation. Ester plasticizers provide the best combination of low-
temperature flexibility, heat resistance, and mechanical properties.
• Chlorosulfonated polyethylene elastomers are used in specialty end-use
applications such as coating, adhesives, roofing membranes, pond and reservoir
liners, electrical wiring, insulation, automotive and industrial hoses, tubingand
belts, and molded goods