Vistalon™ EPDM Rubber

Michael W. Bednarik

VistalonTM EPDM rubber Brand Manager

ExxonMobil Chemical Company (USA)

Nov 18th, 2010

Seminar by BP CHEMICALS - MUMBAI

Specialty Elastomer Product Families

1925 200519651945 1985

1937

1961

1978

1967

19861992

2004

EXXON™ Butyl Rubber

VISTALON™Ethylene-Propylene Rubber

SANTOPRENE™thermoplastic elastomers

VISTAMAXX™propylene-based elastomers

VISTALON™EPDM Rubber

EXXELOR™Modifiers EXACT™

Plastomers

Our roots run deep in synthetic elastomers . . .

... where we’ve been meeting customer needswith innovative elastomeric products

for over 70 years

Vistalon™ EPDM Rubber

• ExxonMobil Chemical is well positioned to support technology advances via combination of proprietary capabilities in either conventional or metallocene EPDM technology• Leading global supplier of Vistalon™ EPDM rubber• Broad range of technologies and products in EPDM industry• Proprietary tailored molecular weight and/or composition distribution

technology, providing improved product attributes and processability• Over 40 years of experience in applications and vanadium-based catalyst

systems • Single-site catalysts• Large polymer design capabilities in solution process

• Extensive patent estate in metallocene technology area• Several commercial metallocene-based EPDM grades

Key Product Attributes

EPDM• Saturated backbone molecule

• Thermal and oxidative stability• Stable to light/UV/air/heat

• Chemical resistance• Good resistance to polar solvents

• Wide range of composition• From low to high ethylene content• From zero to high ENB• Wide range of molecular weight

• Low specific gravity (< 0.9)• Compared to SBR, CR

• Long thin flexible molecule• Can be easily vulcanized• Remains flexible at low temperatures

• Product form• Supplied in bales or pellets

Compounds• Ozone resistance

• Weathering stability (light, UV)

• Heat resistance (up to 160°C)

• Wide durometer range (25A to 40D)

• Electrical resistance

• Low temperature flexibility

• High filler loading leading to cost effective compounds

• Replaced natural and general purpose synthetic rubbers in:• Outdoor applications (automotive profiles,

building profiles, roofing membranes)• Applications where temperature, water and

steam resistance required (coolant hoses, underhood automotive parts, technical hoses)

• Applications where oil resistance not required

EPDM Compounding

Typical EPDM Compound FormulationVistalon™ EPDM Rubber 100 parts per hundred (phr) of rubber

Carbon black Variable phr

Plasticizing oil Variable phr

Diluting fillers (mineral Variable phr

Cure system Variable phr

Typical EPDM Cure SystemsSulfur Peroxide

ZnO 5 phr Coagent (TAC, EDMA) 2 phr

Stearic acid 2 phr Peroxide (Perkadox 14/40, DiCup) 8 phr

Sulfur 0.5 to 2 phr

Primary accelerator (MBT, MBTS) 0.5 to 2 phr

Secondary accelerator (DPTTS, DTDM)(ZDBDC, TDEDC)

0.8 to 3 phr

EPDM Applications

• Electricals• Ozone and corona resistant insulation, stability in water, 105ºC service

rating and flexibility for power cable insulation, cable jackets and connectors

• Molded goods• Flexibility, toughness, abrasion resistance and processability for

mechanical goods such as conveyor rolls, mounts, connectors, gaskets and seals, wheels and brake parts

• Hoses• Good yarn braid adhesion, collapse resistance, cold flexibility, improved

tightness at clamping and improved compression set for industrial air/water/steam, radiators, air brakes and garden hoses

• Automotive profiles• Ozone, heat, UV and tear resistance with weathering stability and good

compression set for window and door seals and body weather seals

• Roof sheeting and pond lining• Good UV resistance with weathering stability, high flexibility and light

weight for roof sheeting

Key Molecular Properties of EP Elastomers

• Composition: C2=, C3=, C6=, C8=, Diene • Copolymer vs. terpolymer (measured by FTIR)

• Molecular weight (measured as Mooney viscosity, melt index)

• Molecular weight distribution (polydispersity, Mw/Mn)• Low molecular weight ends• High molecular weight tail • Gel permeation chromatography

• Compositional distribution• Inter molecular (measured by fractional solubility)• Intra molecular (measured by NMR)

• Long chain branching• Measured by rheology and light scattering

• Polar functionality• Increase compatibility with polar polymers

Wt.

Frac

tion

Wt.

Frac

tion

Log Molecular WeightLog Molecular Weight

84 5 6 73

Narrow

Broad

Structure-Properties: Conventional vs. Metallocene

• Metallocene catalyst• Enable new types of copolymers with desirable performance attributes• Narrow molecular weight distribution

• Maximize physical properties

• Narrow composition distribution

• Efficient comonomer incorporation

Metallocene Catalyst Vanadium Catalyst

Single-Site

Uniform MW /Uniform BranchingM M

M

Multiple Catalytic Sites/Species

Low MW /High Branching

Med MW / Med Branching

High MW /Low Branching

Catalytic Species

A

C

B

Expanded Offering with Metallocene Catalysts

Moo

ney

Visc

osity

Polymer Ethylene Content, Wt%

Finishing0

50

100

0 20 40 60 80 100

MetalloceneCapability

Conventional Z-NCapability

• Conventional Ziegler-Natta (Z-N) catalyst for high MW, bimodal MWD and high ENB grades

• Metallocene catalyst for new EPDM grades with low ethylene, high ethylene, and/or low MW

• Metallocene catalyst allows for production of functional equivalents to conventional Z-N products, but not full drop-in equivalent

• Two platforms are complementary

Metallocene vs. Ziegler-Natta

Metallocene technology• Very low molecular weight capability

• Very low to high ethylene content

• Potential for higher cure state

• Narrow or bimodal composition distribution

• Increased degrees of freedom in polymerization control

• Uniform polymer architecture

• Random distribution

• Low extractables – catalyst residues, calcium stearate, etc.

Conventional technology• Very high molecular weight capability

• Medium to high ethylene content

• Narrow, bimodal or broad composition distribution

• ENB and VNB diene capability

• Sequence distribution of C2 depends on catalyst system

• Composition distribution tailoring via patented reactor technology

EPDM Platforms

Up to 7.5% (ENB) incorporation), efficient cure

From low (10%) to very high (>80%), non-blocky sequences

NarrowMid range, no branching

Very low (ML=5) to max ML=90 at 125ºC (no oil extension possible)

Metallocene

Up to 11%+ (beyond efficiency decrease; other diene possible

From 50 to 80%, random with limited propylene incorporation

Medium to broad and bimodal , LCB

Low (ML= 20 ) to very high (200+) with oil extension

Conventional Z-N

Good high temperature compression set, fast cure rate/high cure state at low diene content

ENB Content

Improved low temperature compression set/flexibility

Ethylene Content

Limited extrusionprocessing, requires blend with broad MWD

MWD

MLRA

Limited low hardness and resilience

MW/Mooney Viscosity

Consequences

Unique Vistalon™ EPDM Bimodal Grades

• Controlled amount of long chain in narrow MWD EPDM branching• High MW ends => influence processing at low shear rates

• High viscosity and high elasticity after extruder die

• Low MW ends => plasticizing effect at high shear rates

• Lower viscosity and reduce elasticity in extruder head

Bimodal MWDNarrow MWD

General illustrations of Bimodal Vistalon EPDM grades

Example Grades:Vistalon 8600 EPDMVistalon 8800 EPDM

Productivity Advantages of Bimodal Vistalon™ EPDM

• Mixing• Higher shear generated for better/faster filler dispersion

• Efficient one-pass mix becomes possible for sponge

• Extrusion• Lower shear generated at high deformation leading to less heat build up

• Higher scorch safety at high strain (die)• Faster screw revolutions possible for faster line speed • More capable extrusion (flow consistency)

• Faster extrusion - lower scrap rate • Faster die change

• Higher elasticity at low shear• Better collapse resistance of soft compounds

• No need of EPDM blend• Better profile geometry control

Vistalon™ EPDM Rubber Grade Slate

0% Diene

0.1-3.4% Diene

3.5-5.9% Diene

>6% Diene

40

50

60

70

80

0 20 40 60 80 100 120 140

ML (1+4) 125ºC

C2 %

7800P1703P

8731

722

706

2504

2504N

404

7001

3708 9301

5601

2727 6505

8600

7500

8800

3666

3702

8700

Compoundingredients

Rubber Extruder

Hot Air Tunnel

Door Seal

Trunk Lid Seal

40º to 100ºC300 to 800 lbs/hr 200 to 250ºC; 2 to 3 min

Mixer

Automotive Body Sealing

• Sponge and dense seal requirements• Collapse resistance and shape retention during vulcanization (sponge)• Complex profile coextrusions with metal or sponge (dense seal)• Fast curing for continuous vulcanization• Fast mixing and extrusion for reduced cycle time

• Key polymer requirements• High diene for fast cure• Bimodal MWD for combination of processability and cure• Low ethylene content for good compression set• Gel-free for smooth profile surface (Class A finish)

ExtruderDual Head Extruder

Conductor Steam Vulcanization Tunnel

125ºC

185ºC / 30 min

125ºC

Jacket

ConductorShield

InsulationNeutralWires

Conductor

Insulation Shield

• Wire and cable requirements• Good wet electrical properties (low power loss through insulation)• Fast extrusion and cure• Tensile strength• Good heat aging

• Key polymer requirements• Minimum residual ionic metal content (clean polymer) for good electrical properties• Low diene content for heat aging.• Reactive diene for peroxide vulcanization • High crystallinity (75% C2) for tensile strength

Electrical Cable Insulation

Roll Up

Black• Oil (tank)• Clay

InternalMixer

EPDM

Cure Mill

Storage

Calender(Sheet Forming 10’ x 100’ )

Splice Table

Mica Dust

6-8 hrs/80-100ºC

Steam Autoclave

(Large Sheets)100’ x 500’

• Roof and geo membrane requirements• Heat aging for long-term service (30+ years)• Processability during calendering• Balance of tack for splicing and green strength for sag resistance• High loading and capacity to hold oil over extended service temperatures

• Key polymer requirements• Low ENB content (about 3%) for long term aging• Tailored MWD for fast processing• Combination of amorphous major polymer fraction (80%) for tack and trace, crystalline minor

polymer fraction (20%) for green strength • Polymer C2 content 69-71 wt. %• Polymer ML (60 to 70) and trace crystallinity (<1.5%) for high loading and oil retention

Sheeting, Roofing, Pond Liners, etc.

InternalMixer

Storage

Part Cutting

Preform Extruder

CompressionTransfer or

Injection Mold

150 to 180ºC

• Brake parts requirements• Fast cure (mainly peroxide)• Low temperature set for operability under cold conditions• Resistance to brake fluid• High tear strength

• Key polymer requirements• Low viscosity (20-25 ML) and slight branching for enhanced processability• ENB content of about 5%• Low ethylene content (45% to 55%) and narrow ethylene CD for enhanced low temperature

properties• Low molecular weight fractions for internal lubrication, since plasticizers will be extracted by fluid• High number average molecular weight for tear and tensile properties

Brake Cups & Diaphragms

Automotive & Industrial Hoses & Belts

160ºC; 15 mInternal

Mixer

Tube Ext

Storage

Knitting Cover Coex

Storage

100ºC;15 m/min 125ºC; 40 m/minpolyester Cut

Steam Autoclave or Salt Bath Coolant Hose

• Automotive hose requirements• Long service life of 150K miles or 10 years• Electrochemically resistant compounds• Good low temperature sealing• Sulfur cure in U.S. and peroxide cure in Europe

• Key polymer requirements• High molecular weight (60 ML) for high-fill compounds• Medium diene level• Broad or tailored MWD for fast extrusion• Minimum crystallinity for collapse resistance and high filler loading • Gel-free for smooth extrusion

Vistalon™ EPDM Applications Summary

Sponge Dense Profiles Stiff Parts Moldings Hoses &

Belts Electricals

Applications• Extruded profiles

• Molding (low or high pressure)

• SG from 0.3 to 0.9

• Auto sealing

• Building profiles

• Sulfur or peroxide cure

• >90 Shore A or 35 to 60 Shore D

• Extruded profiles

• Molded gaskets

• Gaskets

• O-rings

• Mechanical goods

• Appliances

• Hydraulic

• Air

• Steam

• Water

• Insulation

• Medium voltage

• Low voltage

• Jacketing

Key Features

• High oil loading

• High molecular weight

• Collapse resistance

• Low temp flexibility

• Class A surface

• Low temp. flex

• Snappiness

• Extrusion consistent

• Cost effective

• High stiffness

• X-link density

• Low viscosity

• Processing

• High flow

• Low compound

• Viscosity

• High physicals

• Collapse resistance

• Green strength

• Loading

• Aging

• Compression set

• Resistivity

• Loss factor

Vistalon EPDM Bimodal Grades • 8800 • 7500 • 7500

Conventional Vistalon EPDM Grades

• 3666 • 3666• 3666

• 706 (belt)

• 1703P

• 8731

Metallocene Vistalon EPDM Grades

• 5601

• 7001

• New grades• 7001

• 7001

• 2502

• 7001

• 5601

• New grades

• 722

• 7001

Comments

• Bimodal Value• 15% faster mixing cycle• Single-pass mixing• Fast extrusion• Carbon black dispersion• Geometry control• Soft, thin wall• Long term compression set

• New Mcn grades with low C2 content for elasticity and cold properties

• Easy processing

• High rigidity

• Fast curing

• Low shrinkage

• Short injection cycle

• High flow

• Excellent cold properties: V2502

• Fast extrusion

• Compression set

• 1703P – VNB grade for medium voltage insulation

Technical Facilities

Product Testing Labs• Polyolefin testing

• Thermoset testing

• Supporting multiple business units

Thermoset Testing Labs• Basic polymer characterization labs

• Rubber mixing and fabrication• Banbury, milling• Calendering, extrusion• Curing (press, autoclave, CV oven)

• Rubber compound testing

• Rubber vulcanizate testing• Physical, aging, dynamic• Rheology, viscosity (Mooney)• Electrical• Specialty tests

Lab Locations• Baytown, TX, USA

• Bangalore, India

• Brussels, Belgium

Local ATD support also available in China and Japan

State of the Art Capabilities

16%

46%

Advanced Characterization Polymer Laboratories

High Throughput Laboratories

Pilot Plants Large Polymers Testing Lines

Conclusion

• ExxonMobil offers broad range of Vistalon™ EPDM rubber grades for key EPDM markets

• New grades being developed and launched to meet market challenges

• Ongoing investment in EPDM

• Global product and application knowledge to grow and support Vistalon EPDM rubber

Disclaimer

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