Ethylene-Propylene Diene PolyMethylene(EPDM)
EPDM is a synthetic elastomer produced as a copolymer of ethylene and propylene, with small amounts
of a pendant diene (double bonds) in order to cross link the material. Blocks of Ethylene and Propylene
form the backbone of the very long molecule chains of this elastomer (several thousand molecules in
each chain). The diene (usually ENB) is introduced to give reactive sites to tie all these chains together
chemically, during the vulcanization (curing) step.
Because these reactive sites are pendant (not part of the main backbone chain) there are no weak points
on the main chain. This is unlike for example Natural Rubber or SBR, where these necessary reactive
sites are along the main chain. This means that reactive entities in the atmosphere (for example Ozone,
which is very aggressive) can easily attack and degrade these materials. This also explains why EPDM is
on the order of 100 to 1000 times more resistant to ozone than Natural Rubber, even containing
antiozonant stabilizers.
The ethylene and propylene monomers combine to form a chemically saturated, stable polymer backbone
providing excellent heat, oxidation, ozone and weather aging. In consequence ethylene-propylene
rubbers were introduced with a small amount (3-8%) of a third, diene, can be terpolymerized in a
controlled manner to maintain a saturated backbone and place the reactive unsaturation in a side chain
available for vulcanization or polymer modification chemistry. The terpolymers are referred to as EPDM
(or ethylene-propylene-diene with “M” referring to the saturated backbone structure, PolyMethylene). The
EPDM rubbers, whilst hydrocarbon, differ significantly from the diene hydrocarbon rubbers in two principal
ways:
(1) The level of unsaturation is much lower, giving rubbers of much better heat, oxygen and
ozone resistance.
(2) The dienes used are such that the double bonds in the polymer are either on a side chain or
as part of a ring in the main chain. Hence should the double bond become broken the main chain will
remain substantially intact. Dienes commonly used include dicyclopentadiene(DCPD), 4-ethylidene-2-
norbomene(ENB) and hexa-1,4-diene(HD).
The two most widely used diene termonomers are primarily ethylidene norbornene (ENB) followed by
dicyclopentadiene (DCPD). Each diene incorporates with a different tendency for introducing long chain
branching (LCB) or polymer side chains that influence processing and rates of vulcanization by sulfur or
peroxide cures.
Fig. 1 – Structures of Dienes used in EPDM
Termonomer used Cure & Property Features
ENB Low to moderate long chain branching
Fastest & highest state of cure
Good tensile
Good comprerssion set resistance
DCPD High long chain branching
Low sulfur cure
Good comprerssion set resistance
Production
EPDM is produced in a continuous process by
1. Solution polymerization technique
2. Slurry (or suspension) process
3. Gas-phase polymerization.
The majority of product is made using the Ziegler Natta catalysis method, produced usually in the form of
25kg bales, but several producers are now using the alternative and newer metallocene catalysts. These
offer the option of also producing in the form of pellets.
The solution polymerization process is the most widely used in addition to slurry (or suspension)
process & Gas-phase polymerization and is highly versatile in making a wide range of polymers.
Ethylene, propylene are polymerized in presence of catalyst systems in an excess of hydrocarbon
solvent. Stabilizers and oils, if used, are added directly after polymerization. The solvent and un-reacted
monomers are then flashed off with hot water or steam, or with mechanical devolatilization. The polymer,
which is in crumb form, is dried with dewatering in screens, mechanical presses or drying ovens. The
crumb is wrapped into bales or extruded into pellets. The high viscosity, crystalline polymers are sold in
loosely compacted, friable bales or as pellets. The amorphous polymers grades are typically in solid
bales.
Properties
Excellent resistance to heat, oxidation, ozone and weather aging due to their stable, saturated
polymer backbone structure.
Heat aging resistance up to 130°C with properly selected sulfur acceleration systems and heat
resistance at 160°C can be obtained with peroxide cured compounds.
Excellent low temperature flexibility upto - 60°C.
Compression set resistance is good, particularly at high temperatures, if sulfur donor or peroxide
cure systems are used.
good electrical resistivity,
High tensile and tear properties,
Excellent abrasion resistance,
Improved oil swell resistance and resistance to polar solvents, such as water, acids, alkalies,
phosphate esters and many ketones and alcohols.
Producers
Major producers and suppliers of EPDM and EPM are Bayer Polymers, Crompton Corp., Exxon-
Mobil Chemical Co., DSM Elastomers, Dupont Dow Elastomers, Herdillia, JSR, Kumho Polychem, Mitsui
Chemicals, Polimeri Europa, and Sumitomo Chemical Co. Wide ranges of grades are available worldwide
to provide solutions to many product requirements.
Applications
Versatility in polymer design and performance has resulted in broad usage in automotive
weather-stripping and seals, glass-run channel, radiator, garden and appliance hose, tubing, belts,
electrical insulation, roofing membrane, rubber mechanical goods, plastic impact modification,
thermoplastic vulcanizates and motor oil additive applications.
