The Global Innovative EPDM supplier Keltan ® EPDM Innovative and Surprising after all these years Herman Dikland.

The Global Innovative EPDM supplier

Keltan® EPDMInnovative and Surprising after all these years

Herman Dikland


Content

• Historical perspective– Catalysis– Technology– Applications– Keltan® history

• Keltan® Innovations– Keltan ACE™ technology– REX technology– New product development

• Concluding remarks


Historical Perspective


Historical perspective … Ziegler-Natta Catalysis

• 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

It took more than 40 years…


Historical perspective … Ziegler-Natta Catalysis

• PP and EPDM development– Research communities

– Dissemination of knowledge

– Industrial relevance

• PE and PP ahead of EPDM– 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)

Source: M.A. Rappa and K. Debackere

A.P. Sloan School of Management (1990)


Historical perspective … Advanced Catalysis

• Metallocene catalysts: Metal sandwiched between two cyclopentadiene (Cp) ligands– 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• MAO activates, scavenges, stabilizes and prevents bi-

metallic deactivation…

• After Kaminsky’s breakthrough– 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


Historical perspective … Technology

• 1960 – 1980– First EPDM plants erected in the early sixties

– Typical plant scale 5 – 15 ktpa

– Slurry and solution processes

• 1980 – 2000– Debottlenecking

– Implementation of deep cooling technology

– New finishing technology

• 2000 – 2010– New large scale facilities (60 – 100 ktpa)

– Gas phase technology (†)

– Dry finishing technology

– Post-reactor modification technology


Historical perspective … Applications

• Initial target application for EPDM was in tires– Poor building tack

– Poor abrasion resistance

– Poor dynamical properties

• Today, #1 synthetic rubber for non-tire, non-latex applications– 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:– Plastomers and reactor TPO (W&C and PP impact modification)

– TPVs in automotive sealing systems



• 70’s: Automotive sealing systems NR/CR/SBR• 80’s: Window gaskets PVC/SBR/caulks• 80’s: Coolant hoses CR/NBR• 80’s: Bull eyes SBR• 80’s: Petroleum additives Poly(methacrylates)• 90’s: Roof sheeting PVC/bitumen• 90’s: Exhaust mounts NR/CR/VMQ• 90’s: Potable water seals SBR• 00’s: V-belts CR• 00’s: Wastewater seals SBR



• 10’s: Ongoing substitution– Windshield wipers NR/CR

– Engine mounts NR

– Grass infill NR reclaim

– Ultra-low density insulation sponge PVC-NBR/LDPE

• Continued growth– With automotive build and GDP

– Topped with continued inter-material substitution

• More than 1000 ktpa global demand


Historical perspective … Keltan®

1960 Start research activities1965 Obtained license for Ziegler-Natta catalysts1966 Established Keltan® trademark1967 Start up EPT 1, Geleen1973 Start up EPT 2, Geleen1974 EPT 1 stop1975-8 Debottlenecking EPT 21981 EPT 1 re-start1982 First computer in EPT1983 Introduction of promoted catalyst systems


Historical perspective … Keltan®

1988 Debottlenecking EPT 11989 Acquisition Copolymer (Addis, US)1991 JV DSM-Idemitsu Company (Chiba, Japan)1996 Acquisition Nitriflex (Triunfo, Brazil)2003 Startup EPT 3, Geleen2004 Closure plants in Addis and Chiba 2005 Debottlenecking EPT 1-22005 Debottlenecking EPT 32007 Start up large-scale reactive extrusion line in Triunfo2008 Implementation Keltan ACE™ technology2009 Introduction first high-VNB products, Keltan DE8270C


Keltan Innovations®


Innovations … Keltan ACE™ Technology

• Cutting edge advanced catalyst technology– High catalyst efficiency …………………….…….…………. …..orders of magnitude

– Higher polymerization temperatures ………............. less cooling, higher solids

– Higher selectivity towards -olefins ………………………product diversification

– Product differentiation opportunities ………………….…. high VNB, and more…

• Sustainable benefits, in terms of– Product diversification opportunities

– Investment for grass root plant

– No catalyst waste products

– Improved energy utilization


Innovations … Keltan ACE™ high-VNB products

Lower residual peroxide in end

product

Significantly improved

compression set properties

Properties related to crosslink

densitiy improve (ageing,

chloramine resistance)

Peroxide Crosslinking

Less peroxide and/or coagent

Higher total loading level (Phr) while

maintaining compression set

properties

No change in peroxide No change in filler

level

Less Peroxide decomposition

products

Less volatile emissions

(VOC)

Improved higher T compression set

values

Hperbranched structure

Improved processing (better

flow)

Peroxide curing efficiency

VNB >DCPD/ENB

or or

Improved heat ageing resistance (5-10 °C compared

to NEN/DCPD)1

Lower 3rd monomer level

Increased Scorch time

Less PP degradationIn TPV application

Improved fiber/cord/fabric

adhesion

Higher cross link density

Lower compound

cost

Enhanced electrical insulation

Fogging reduction

Bloom reduction

Odor reduction (processing and

end use)

Less stresscracking

Improved snappiness

No black scorch

Lower post curing necessary

Enhanced compound elasticity


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


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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K740 pure 90/10phr 80/20phr 70/30phr 60/40phr 50/50phr

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T.S. [MPa] Hardness [°Sh.A] Tear str. Delft [N] Elongation [%] MLVis

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[%]


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


Concluding Remarks

• 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 leastAt least

The Global Innovative EPDM supplier Keltan ® EPDM Innovative and Surprising after all these years Herman Dikland.

Documents

epdm catalyst efficiencies

epdm plants

exxon slide

catalyst productivity

mao cocatalyst mao

tea cocatalyst

polyolefin catalyst

years herman dikland