Innovative High Performance ACE™ EPDM polymers

Gosé van Zandvoort, Global R&D/TS&AD - EPDM LANXESS Business Unit Technical Rubber Products

Mobility Days Prague, November 22, 2012

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Innovative high performance ACE™ EPDM polymers

  Introduction New ACE™ catalyst technology

 Experimental section

 Results:

-  Polymer composition & structure

-  Mixing and rheometer data

-  Physical compound properties

 Conclusions

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New innovations in EPDM production

ethylene

C H 2 C H 2

propylene

C H C H 2

H 3 C

diene as termonomer (e.g. ENB)

Keltan ACE™ technology

EPDM

EPM

New Catalyst Technology!!

Instead of Ziegler-Natta

Bio based!!

=

Keltan® ECO

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Introduction Keltan ACE™ Technology

  Keltan ACE™ technology is based on a specific family of advanced catalysts licensed from NOVA

  The technology has been further refined during eight years of catalyst development

  A new catalyst family for EPDM production has been developed and patent-protected by LANXESS

  Keltan ACE™ is a key technology to achieve the sustainability vision of LANXESS and an enabler for EPDM capacity expansion projects

Showing long-term commitment to the EPDM market

2009 - 2012

Various Keltan ACE™ runs

Market being sampled

2008

Large-scale validation of Keltan ACE™ technology

2013

Full conversion of biggest EPDM plant

in Geleen to ACE

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Benefits of Keltan® ACE™ technology

Innovation Sustainability Reduced energy requirement   Less pressure on increasingly scarce resources No catalyst waste   No deashing necessary, yet lower catalyst

residues Chlorine free product   Avoidance of chlorine in catalyst system resulting

in lower contact corrosion

Full grade slate capability   Unique ability to produce the same high quality

grades regardless of catalyst technology Product diversification potential   Breakthrough for peroxide vulcanized compounds

with the High VNB technology platform   Enabling reduced peroxide dosage, improved

properties or increased compound loading

Keltan® ACE™

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Objective Polymer Compound Study

  Over the past years it seemed challenging to achieve excellent Ziegler-Natta like product performance with new (post-)metallocene catalysts

  Aim of this study

-  To prove that the Keltan ACE™ technology is capable to produce a complete range of EPDM polymers with equal properties as their Keltan® Ziegler-Natta counter types

-  To prove that the Keltan ACE™ technology covers the whole EPDM product range

  Text (16 pt) LANXESS EPDM Production Site in Geleen,

The Netherlands

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Experimental Section

Standard product development evaluation Broad selection of Ziegler-Natta products   Three sets of 2 EPDM polymers were studied

  3 polymers are commercially available and are produced with generic Ziegler-Natta catalyst

  3 analogues have been produced with Keltan ACE™ technology in the pilot plant

  Polymers were analyzed with FT-IR, GPC and DSC   Level of Long Chain Branching (LCB) was

measured with DMS   The polymers were evaluated in a standard

compound, which was mixed with an intermeshing mixer

  Physical properties were tested on EPDM vulcanizates

  (Ageing conditions: 168 hrs @ 100 °C (ISO 188)

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Broad selection of Ziegler-Natta products From multi-purpose to high performance

Trade Name Polymer Characteristics Application area

Polymer 1 Keltan® 8550 Amorphous

Medium ENB

Long Chain Branched

• Fast mixing and extrusion • All-round EPDM used in e.g. dense profiles,

radiator hoses, window gaskets

Polymer 2 Keltan® 6951 Amorphous

Oil extended

Very high Mooney

Very high ENB

Long Chain Branched

• Good mixing, ultra fast vulcanization and excellent physical properties, like collapse resistance.

• Best in class for automotive sponge seals

Polymer 3 Keltan® 5469 Semi-crystalline

Oil extended

Extremely high Mol. Weight

• Suitable for production of high performance parts and for mechanical goods with high compound

Loading

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EPDM Polymer Composition & Structure C2 content adjusted to match the crystallization behavior

EPDM Polymer ZN1 ACE1 ZN2 ACE2 ZN3 ACE3

Catalyst system Ziegler- Natta

Keltan ACE™

Ziegler- Natta

Keltan ACE™

Ziegler- Natta

Keltan ACE™

ML(1+4)125 °C [MU] 80 80 63 63 52 52

C2 [wt%] 55 48 48 44 63 58

ENB [wt%] 5.5 5.5 9.0 9.0 4.5 4.5

Oil [wt%] 0 0 13 13 50 50

Mw/Mn [-] 3.2 3.3 3.1 3.4 3.0 3.1

Δδ [°] 16 14 18 18 31 28

Cryst.temp. [°C] -34 -38 -48 -41 -22 -25

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Polymer ZN1 ACE1 C2 [wt%] 55 48 Cryst.temp. [°C] -34 -38

Polymer ZN1 ACE1 Mn [kg/mol] 95 100 Mw [kg/mol] 290 330 Mw/Mn [-] 3.2 3.3

GPC and Crystallization Curves Polymer ZN1 & ACE1 Perfect match between ZN- and ACE polymer

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Polymer ZN2 ACE2 C2 [wt%] 48 44 Cryst.temp. [°C] -48 -41

Polymer ZN2 ACE2 Δδ [°] 18 18

DMS and Crystallization Curves Polymer ZN2 ACE2 Perfect match between ZN- and ACE polymer

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Ingredient [phr] ZN1 / ACE1 ZN2 / ACE2 ZN3 / ACE3 EPDM 100 115 200 ZnO 5 5 5 Stearic acid 1 1 1 Carbon black N-550 70 70 70 Carbon black N-772 40 40 40 Oil 70 55 0 MBTS-80 1,31 1,31 1,31 ZBEC-70 0,7 0,7 0,7 ZDBP-50 3,5 3,5 3,5 Vulkalent E/C 0,5 0,5 0,5 S-80 1,25 1,25 1,25 Total phr 293,26 293,26 323,26

Standard Compound Evaluation in a “70-40-70” recipe Polymer rich compound – oil correction oil-extended grades

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EPDM Polymer ZN1 ACE1 ZN2 ACE2 ZN3 ACE3

ML(1+4)100 °C [MU] 59 57 61 61 71 75

Scorch t5 [min] 29 30 29 31 37 32

Rheometer data

Ts2 [min] 1.2 1.2 1.2 1.2 1.5 1.5

T90 [min.] 4.7 4.8 3.8 3.7 5.3 5.4

State of cure ΔS MH-ML [dNm]

15 15 15 14 11 11

Mooney, Mooney Scorch and Rheometer Data Curing package does not need adjustment

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Polymer ZN3 ACE3 ML(1+4)100 °C [MU] 71 75

Scorch t5 [min] 37 32

Polymer ZN3 ACE3 Ts2 [min] 1.5 1.5 T90 [min.] 5.3 5.4 MH-ML [dNm] 10.6 11.4

Mixing- Rheometer curves compounds ZN3 & ACE3 Perfect match ZN & ACE-polymer

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EPDM Polymer ZN1 ACE1 ZN2 ACE2 ZN3 ACE3

IRHD Hardness [-] 64 63 64 65 55 54

M100% [MPa] 2.8 2.9 3.2 3.3 1.9 1.8

M300% [MPa] 10 10 11 11 7 7

TS [MPa] 14 15 13 13 18 18

EB [%] 486 469 375 394 613 628

Tear [N] 42 44 42 45 43 42

CS @ -25°C [%] 33 33 25 32 83 77

CS @ 100°C [%] 18 24 15 17 35 34

Physical Properties EPDM Vulcanizates Similar crystallinity & similar X-link density Similar properties

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Median Tensile Curves for Vulcanizates from ZN3 and ACE3 Perfect match ZN- & ACE-polymer

 Tensile curves are identical for ZN- and ACE-analogues

 Again proof that the polymer structure and the crystallinity are very similar for the ZN- and ACE analogues

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EPDM Polymer ZN1 ACE1 ZN2 ACE2 ZN3 ACE3 IRHD Hardness [-] 64 63 64 65 55 54 Δ IRHD after aging [-] +5 +5 +4 +5 +6 +7 M100% [MPa] 2.8 2.9 3.2 3.3 1.9 1.8 M100% after aging [MPa] 4.2 4.2 4.3 4.7 3.2 3.2 M300% [MPa] 10 10 11 11 7 7 M300% after aging [MPa] 13 13 13 13 12 12 TS [MPa] 14 15 13 13 18 18 TS after aging [MPa] 14 13 13 13 13 14 EB [%] 486 469 375 394 613 628 EB after aging [%] 360 311 303 295 338 346

Physical Properties for the EPDM Vulcanizates after Aging The effect of heat aging is not negatively affected by the choice of catalyst

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ACE™ high performance polymers

Most advanced metallocene production technologies for EPDM have their limitations in Mooney viscosities (20-80 MU) and ENB content (usual

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