Keltan® EPDM
Innovative and Surprising after all these years
Herman Dikland
The Global Innovative EPDM supplier
Content
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Historical perspective
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Catalysis
Technology
Applications
Keltan® history
Keltan® Innovations
– Keltan ACE™ technology
– REX technology
– New product development
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Concluding remarks
The Global Innovative EPDM supplier
Historical Perspective
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Historical perspective … Ziegler-Natta Catalysis
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Von Pechmann, linear PE, a laboratory curiosity (1906)
ICI, high-pressure polyethylene (~ 1935)
Ziegler, Max-Planck ‘Kohlenforschung’ low-pressure linear PE (~
1953): ‘Mülheimer Chemie'.
Natta, Polytechnico di Milan, stereoregular PP (~ 1953)
Less successful alternatives: Standard Oil (Mb catalyst) and Philips
Petroleum (Cr catalyst)
Ziegler and Natta Nobel Prize winners in 1963
Increased industrial importance starting in early sixties
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It took more than 40 years…
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Historical perspective … Ziegler-Natta Catalysis
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PP and EPDM development
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Research communities
Dissemination of knowledge
Industrial relevance
PE and PP ahead of EPDM
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Catalyst efficiencies improved
orders of magnitude
New production technologies
developed
Economies of scale developed
Early introduction of advanced
catalyst systems
Source: M.A. Rappa and K. Debackere
A.P. Sloan School of Management (1990)
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Historical perspective … Advanced Catalysis
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Metallocene catalysts: Metal sandwiched between two
cyclopentadiene (Cp) ligands
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First invented in 1951 (!): simple ferrocenes, Cp2Fe
Natta published results on Cp2TiCl2 with TEA co-catalyst in
1957
Accidental discovery by Kaminsky of Cp2ZrCl2 with MAO
co-catalyst
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After Kaminsky’s breakthrough
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MAO activates, scavenges, stabilizes and prevents bimetallic deactivation…
Focus on commercialization
Improving MAO:metal ratio’s
Development of alternative co-catalysts
Increasing catalyst productivity
Over 1 billion USD has been spent in polyolefin catalyst
research by Dow and Exxon
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Historical perspective … Technology
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1960 – 1980
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1980 – 2000
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First EPDM plants erected in the early sixties
Typical plant scale 5 – 15 ktpa
Slurry and solution processes
Debottlenecking
Implementation of deep cooling technology
New finishing technology
2000 – 2010
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New large scale facilities (60 – 100 ktpa)
Gas phase technology (†)
Dry finishing technology
Post-reactor modification technology
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Historical perspective … Applications
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Initial target application for EPDM was in tires
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Today, #1 synthetic rubber for non-tire, non-latex applications
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Poor building tack
Poor abrasion resistance
Poor dynamical properties
Excellent wheatherability
Excellent processability and filler tolerance
Broad temperature performance window (-40 °C up to 140 °C)
Excellent cost:performance ratio
Gradual replacement of NR, SBR and CR in standard rubber
applications
Hardly any substitution by other materials. Exceptions:
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Plastomers and reactor TPO (W&C and PP impact modification)
TPVs in automotive sealing systems
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Historical perspective … Applications
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70’s: Automotive sealing systems
80’s: Window gaskets
80’s: Coolant hoses
80’s: Bull eyes
80’s: Petroleum additives
90’s: Roof sheeting
90’s: Exhaust mounts
90’s: Potable water seals
00’s: V-belts
00’s: Wastewater seals
NR/CR/SBR
PVC/SBR/caulks
CR/NBR
SBR
Poly(methacrylates)
PVC/bitumen
NR/CR/VMQ
SBR
CR
SBR
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Historical perspective … Applications
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10’s: Ongoing substitution
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NR/CR
NR
NR reclaim
PVC-NBR/LDPE
Continued growth
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Windshield wipers
Engine mounts
Grass infill
Ultra-low density insulation sponge
With automotive build and GDP
Topped with continued inter-material substitution
More than 1000 ktpa global demand
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Historical perspective … Keltan®
1960
1965
1966
1967
1973
1974
1975-8
1981
1982
1983
Start research activities
Obtained license for Ziegler-Natta catalysts
Established Keltan® trademark
Start up EPT 1, Geleen
Start up EPT 2, Geleen
EPT 1 stop
Debottlenecking EPT 2
EPT 1 re-start
First computer in EPT
Introduction of promoted catalyst systems
The Global Innovative EPDM supplier
Historical perspective … Keltan®
1988
1989
1991
1996
2003
2004
2005
2005
2007
2008
2009
Debottlenecking EPT 1
Acquisition Copolymer (Addis, US)
JV DSM-Idemitsu Company (Chiba, Japan)
Acquisition Nitriflex (Triunfo, Brazil)
Startup EPT 3, Geleen
Closure plants in Addis and Chiba
Debottlenecking EPT 1-2
Debottlenecking EPT 3
Start up large-scale reactive extrusion line in Triunfo
Implementation Keltan ACE™ technology
Introduction first high-VNB products, Keltan DE8270C
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Keltan Innovations®
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Innovations … Keltan ACE™ Technology
• Cutting edge advanced catalyst technology
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High catalyst efficiency …………………….…….…………. …..orders of magnitude
Higher polymerization temperatures ………............. less cooling, higher solids
Higher selectivity towards a-olefins ………………………product diversification
Product differentiation opportunities ………………….…. high VNB, and more…
• Sustainable benefits, in terms of
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Product diversification opportunities
Investment for grass root plant
No catalyst waste products
Improved energy utilization
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Innovations … Keltan ACE™ high-VNB products
Peroxide
Crosslinking
Increased
Scorch time
Peroxide curing
efficiency
VNB >DCPD/ENB
Less peroxide and/or
coagent
Less Peroxide
decomposition
products
Less volatile
emissions
(VOC)
Odor reduction
(processing and
end use)
Bloom reduction
Fogging
reduction
Enhanced
electrical
insulation
or
Higher total loading
level (Phr) while
maintaining
compression set
properties
Lower residual
peroxide in end
product
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No change in peroxide
No change in filler
level
Higher cross link
density
Lower 3rd
monomer level
Less PP degradation
In TPV application
Improved heat
ageing resistance
(5-10 °C compared
to NEN/DCPD)1
Lower post curing
necessary
Less stress
cracking
Enhanced
compound elasticity
Improved
processing (better
flow)
No black
scorch
Lower
compound
cost
Improved higher T
compression set
values
Hperbranched
structure
Improved
fiber/cord/fabric
adhesion
Significantly
improved
compression set
properties
Properties related
to crosslink
densitiy improve
(ageing,
chloramine
resistance)
Improved
snappiness
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Innovations … REX Technology
• Ethylene-propylene copolymers are used in petroleum additive
applications for more than 30 years
– Viscosity Index Improvement (VII)
– Soot dispersant control
• Specialty products are made by post-reactor modification
• In 2008 DSM started operating the largest reactive extrusion plant in
its kind in Triunfo, Brazil
• Key products for VII applications are
– Keltan 1200A
– Keltan 3200A
• Keltan 1200A also suitable for
– V belts, potable water applications,
brake parts, food contact applications
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Innovations … K1200A: The Ultra-Low Viscosity Grade
• High-hardness and polymer-rich formulations are difficult to process
• Keltan 1200A can be used as blend partner
Compound viscosity sharply reduced
Extractables are markedly reduced (vs. traditional processing aids)
Hardness, tear and tensile properties are largely maintained
Microbial growth properties are improved
Retention of properties after high-temperature ageing is improved
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Elongation [%]
Viscosity [mu], Hardness [ShA], Tensile [MPa], Tear [N]
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50
20
10
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K740 pure
T.S. [MPa]
90/10phr
80/20phr
Hardness [°Sh.A]
70/30phr
Tear str. Delft [N]
60/40phr
50/50phr
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Elongation [%]
ML
Innovations … New Products
• Conversion of standard paraffinic oil to high quality
colorless oils in oil-extended products
– Keltan 4551A (former K509x100), Keltan 6531A (former K708x15)
and Keltan 4331A (former K512x50)
• Broadest array of products for sponge automotive sealing
systems
– Keltan 4703, Keltan 4903, Keltan 7341A, Keltan 6251A
• Best-in-class quality products for TPV applications
– Keltan 5531A, Keltan 4551A, Keltan 7341A
• New product for automotive solid sealing systems
– Keltan 8642A
• New Keltan ACE™ grade for peroxide cure applications
– Keltan DE8270C
The Global Innovative EPDM supplier
Concluding Remarks
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It took 40 years to understand the value of von Pechmann’s invention
It took another 40 years to establish EPDM as #1 synthetic rubber for
general purpose rubber applications
It will take another 40 years before EPDM becomes a true commodity
At least
The Global Innovative EPDM supplier