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

VISTAMAXX propylene-based elastomers 2004

EXXON Butyl Rubber 1937

VISTALON Ethylene-Propylene Rubber 1961 SANTOPRENE thermoplastic elastomers 1978

1925

1945

1965

1985
1986

2005

Our roots run deep in synthetic elastomers . . .

1967 VISTALON EPDM Rubber

1992 EXXELOR Modifiers EXACT Plastomers

... where weve been meeting customer needs with 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

Compounds Ozone resistance Weathering stability (light, UV) Heat resistance (up to 160C) 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

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

EPDM Compounding
Typical EPDM Compound Formulation
Vistalon EPDM Rubber Carbon black Plasticizing oil Diluting fillers (mineral Cure system 100 parts per hundred (phr) of rubber Variable phr Variable phr Variable phr Variable phr

Typical EPDM Cure Systems

Sulfur ZnO Stearic acid Sulfur Primary accelerator (MBT, MBTS) Secondary accelerator (DPTTS, DTDM) (ZDBDC, TDEDC) 5 phr 2 phr 0.5 to 2 phr 0.5 to 2 phr 0.8 to 3 phr Peroxide Coagent (TAC, EDMA) Peroxide (Perkadox 14/40, DiCup) 2 phr 8 phr

EPDM Applications
Electricals
Ozone and corona resistant insulation, stability in water, 105C 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)

Wt. Fraction

Broad

Narrow

Long chain branching

Measured by rheology and light scattering

Polar functionality
Increase compatibility with polar polymers

Log Molecular Weight

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

Single-Site

Vanadium Catalyst
Multiple Catalytic Sites/Species
Med MW / Med Branching Catalytic Species
A C B

M M

Uniform MW / Uniform Branching

Low MW / High Branching

High MW / Low Branching

Expanded Offering with Metallocene Catalysts

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
100

Conventional Z-N Capability

Mooney Viscosity

Metallocene Capability

50

Finishing

0 0 20 40 60 80 100

Polymer Ethylene Content, Wt%

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
Conventional Z-N
MW/Mooney Viscosity Low (ML= 20 ) to very high (200+) with oil extension

Metallocene
Very low (ML=5) to max ML=90 at 125C (no oil extension possible) Narrow Mid range, no branching From low (10%) to very high (>80%), non-blocky sequences Up to 7.5% (ENB) incorporation), efficient cure

Consequences
Limited low hardness and resilience

MWD MLRA Ethylene Content

Medium to broad and bimodal , LCB From 50 to 80%, random with limited propylene incorporation Up to 11%+ (beyond efficiency decrease; other diene possible

Limited extrusion processing, requires blend with broad MWD Improved low temperature compression set/flexibility

ENB Content

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

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

Example Grades:
Vistalon 8600 EPDM Vistalon 8800 EPDM

Bimodal MWD Narrow MWD

General illustrations of Bimodal Vistalon EPDM grades

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

C2 %
80
7800P 1703P 8731 7001 722 3708 3702 706 8700

0% Diene 0.1-3.4% Diene 3.5-5.9% Diene >6% Diene

70

9301 5601

60

3666 8600

2504 2504N 6505

2727

7500 8800

50
404

40 0 20 40 60 80 100 120 140

ML (1+4) 125C

Automotive Body Sealing

Compound ingredients Mixer Hot Air Tunnel
40 to 100C 300 to 800 lbs/hr 200 to 250C; 2 to 3 min

Rubber Extruder Door Seal

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 Trunk Lid Seal Fast mixing and extrusion for reduced cycle time 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)

Key polymer requirements

Electrical Cable Insulation

Dual Head Extruder Neutral Wires Extruder
125C 125C

Insulation Conductor

185C / 30 min Conductor Shield

Conductor

Steam Vulcanization Tunnel Jacket

Insulation Shield

Wire and cable requirements

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

Key polymer requirements

Sheeting, Roofing, Pond Liners, etc.

Black Oil (tank) Clay Storage
EPDM Cure (Large Sheets) 100 x 500

Internal Mixer Mill Calender

Roll Up
6-8 hrs/80-100C Steam Autoclave Mica Dust

Splice Table

(Sheet Forming 10 x 100 )

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

Brake Cups & Diaphragms

Storage Part Cutting Internal Mixer Preform Extruder Compression Transfer or Injection Mold 150 to 180C

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

Automotive & Industrial Hoses & Belts

Storage Internal Mixer Storage

100C;15 m/min

polyester Knitting

125C; 40 m/min

Cut

160C; 15 m

Tube Ext

Cover Coex

Steam Autoclave or Salt Bath

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 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

Coolant Hose

Key polymer requirements

Vistalon EPDM Applications Summary

Sponge
Extruded profiles Applications Molding (low or high pressure) SG from 0.3 to 0.9

Dense Profiles
Auto sealing Building profiles Sulfur or peroxide cure Class A surface Low temp. flex Snappiness Extrusion consistent Cost effective

Stiff Parts
>90 Shore A or 35 to 60 Shore D Extruded profiles Molded gaskets

Moldings
Gaskets O-rings Mechanical goods Appliances Processing High flow Low compound Viscosity High physicals

Hoses & Belts

Hydraulic Air Steam Water Collapse resistance Green strength Loading Aging Compression set 7500 3666 706 (belt) 7001 5601 New grades

Electricals
Insulation Medium voltage Low voltage Jacketing

High oil loading Key Features High molecular weight Collapse resistance Low temp flexibility

High stiffness X-link density Low viscosity

Resistivity Loss factor

Vistalon EPDM Bimodal Grades Conventional Vistalon EPDM Grades Metallocene Vistalon EPDM Grades

8800

7500

3666

3666

1703P 8731 722 7001

5601 7001 New grades Bimodal Value 15% faster mixing cycle Single-pass mixing Fast extrusion Carbon black dispersion Geometry control Soft, thin wall Long term compression set 7001

7001 2502

Easy processing New Mcn grades with low C2 content for elasticity and cold properties High rigidity Fast curing Low shrinkage

Short injection cycle High flow Excellent cold properties: V2502

Fast extrusion Compression set

Comments

1703P VNB grade for medium voltage insulation

Technical Facilities
Product Testing Labs
Polyolefin testing Thermoset testing Supporting multiple business units

Lab Locations
Baytown, TX, USA Bangalore, India Brussels, Belgium Local ATD support also available in China and Japan

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

State of the Art Capabilities

16%
Advanced Characterization Polymer Laboratories

46%

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

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