Plasticizers for the Rubber Industry –Legislations, Regulations and the

Consequences

VKRT Meeting

2007-12-13

Jürgen Trimbach

Hansen & Rosenthal

Page 2

Agenda

� Short Introduction of H&R

� Historical overview

� Plasticizers and Legislation

� Actual Activities

� Conclusion

Page 3

Who´s H&R?

H&R WASAG Group

2003 2004 2005 2006Sales: 211.2m 550m 565m 820m

Chemical/pharmaceuticalraw materials

Sales: 700 m€

Further growth through acquisition and expansion

of capacity

Leading market positions in Europe and Asia

Technology leader

Precision plastics

Sales: 55 m€

Further growth through building up new sites

worldwide

Technology leader

Page 4

Who´s H&R?

The Rubber Industry needed in 2005:

22.000.000 mt rubber (NR, SBR, BR, EPDM, IIR, CR, NBR, …)

16.000.000 mt fillers (Carbon Black, Silica, Clay, Whiting, …)

8.000.000 mt steel and cord

3.000.000 mt plasticizer (DAE, PAR, NAP, MES/TDAE, …)

450.000 mt Sulphur

400.000 mt ZnO

150.000 mt Ozon protecting waxes

1.000.000 mt other chemical specialties

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Who´s H&R?

The Rubber Industry needed in 2005:

22.000.000 mt rubber (NR, SBR, BR, EPDM, IIR, CR, NBR, …)

16.000.000 mt fillers (Carbon Black, Silica, Clay, Whiting, …)

8.000.000 mt steel and cord

3.000.000 mt plasticizer (DAE, PAR, NAP, MES/TDAE, …)

450.000 mt Sulphur

400.000 mt ZnO

150.000 mt Ozon protecting waxes

1.000.000 mt other chemical specialties

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Who´s H&R?

Tank farm forProcess oils

Sales office

Production andTank farm forProcess oils

Blend plant

New

projects

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One short Word

Because of Mrs. Elise Goedhart – van der Hout´sREACH presentation, Mr. Karl Ehlert´s paper„Legislation on food contact materials in theNetherlands, European Union and USA “ and otherlectures I will focus my presentation on AromaticPlasticizers.

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� Historical overview

� Plasticizers and Legislation

� Actual Activities

� Conclusion

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Approx. 4.000 B. C.

Τεν Τεν Τεν Τεν λαωσλαωσλαωσλαωσ ωερεωερεωερεωερε ενουγηενουγηενουγηενουγη

Page 10

Approx. 0

Some 200 lawsconcerningproduction, tradingand taxes

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1875

We never had so nice

libraries to conceal the

laws.

In Prussia now approx.

1.000 laws and

regulations concerning

production, trading and

taxes, but also the first

safety regulations.

Page 12

Approx. 1920

It has been proved that

polycondensated aromatic

rings can cause cancer,

especially lung and skin

cancer.

PCAs in measurable

amounts, e. g. from

Creasote, are forbidden in

the food and medical

industry.

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1960

DAE – Distillated AromaticExtract - has to besubstituted in printing inkapplications because of ist carcenoginic potential

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1992 – 2005/2010

EU Substance Directive 1967/548/EC and EU Preparations Directive 1999/45/EC including adaptations to technical progress:

1992 All distillate aromatic extracts (DAE) are classifiedas carcinogens; label “T” and “R45” risk phrase

1994 Other process oils with ≥≥≥≥ 3 % PCA (IP 346) are classified as carcinogens with labels “T” and “R45” *

1996 All low viscous process oil <7 mm2/s are labelledwith risk phrase “R65” (“May cause lung damage ifswallowed”)

mid 2002 Environmental risk phrase “R53” for DAE (“May causelong-term effects in aquatic environment”)

mid 2005 EU Directive 76/769/EEC (PAHs in tyres) is agreed

December 9 2005 the Directive is signed by the EU Parlament and published

01.01.2010 All tires in Europe, imported or produced in the EU, have to fullfill the DIRECTIVE 2005/69/EC OF THE EUROPEAN PARLIAMENT AND OF THE COUNCIL

Page 15

2007

H&R expands its Hamburg refinery

– plus 80.000 t noncarcino-genic plasticizers –

and has to follow 86 laws, regulations and prescriptions and to fill 112 folders with 33.600 pages of paper for the authorities.

Page 16

� Historical overview

� Plasticizers and Legislation

� Actual Activities

� Conclusion

Page 17

DIRECTIVE 2005/69/EC

… Furthermore, the tyresand treads for retreadingmanufactured after 1 January 2010 may not beplaced on the market ifthey contain extender oilsexceeding the limits indicated in paragraph 1. …

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The Requirements

Plasticizers for tyres have to fullfill:

IP 346 < 3,0 %B(a)P < 1 ppm or8 Grimmer PCAs < 10 ppmBP NMR < 0,35

No exceptions allowed – no aviation, racing or specialindustry tyre

Plus

Mutagenicity Index < 1

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DMSO Extraction (IP 346)

Sample + Cyclohexane, DMSO

+ Cyclohexane+ H2O/NaCl

+ H2O

+ Cyclohexane

Page 20

DMSO Extraction (IP 346)

Sample + Cyclohexane, DMSO

+ Cyclohexane+ H2O/NaCl

+ H2O

+ Cyclohexane

Page 21

Individual PCAs (GC-MS)

Pre-treated sample

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Individual PCAs (GC-MS)

Page 23

Bay Proton NMR (ISO 21461)

Definition of PCA (= PAH, PNA, PKA, …):

Polycyclic aromatic hydrocarbons are organic compoundsconsisting of two or more aromatic rings where certain carbonatoms are common to two, three or more rings.

The name hydrocarbon indicates that the molecule containsonly carbon and hydrogen.

Page 24

Bay Proton NMR (ISO 21461)

x 100HBay =I1 + I3

I2

� Extraction with Acetone

� Oil to disolve in CDCl3

� NMR spectrum, calculation

I1 = Pure Aromatic area

I2 = Bay region defined from 8,3 ppm to 9,50 ppm

I3 = Aliphatic and ethylenic regions defined from 0,2 ppm to 5,8 ppm

H = percentage of Bay protons

Page 25

Bay Proton NMR (ISO 21461)

Benzo-(a)-pyrene H

H

Bay region

CH3

5-Methylchrysene(not in the Grimmrer substancies)

H

H

H

Bay region

Page 26

Bay Proton NMR (ISO 21461)

CH3

Methylnaphthaline

Page 27

Bay Proton NMR (ISO 21461)

H

C

Methylnaphthaline

H

H

H

Bay region

S

Benzo-(a)-thiopyrene H

H

Bay region

Definition of PCA:

…. The name hydrocarbon indicates that themolecule contains only carbon and hydrogen.

Page 28

� Historical overview

� Plasticizers and Legislation

� Actual Activities

� Conclusion

Page 29

Legal Defaults - Consequences

DAE for tires has to be substituted by alternative oils asap!

The worldwide consumption is 1.000.000 tons per year!The consumption in Europe is 300.000 tons, in Asia 400.000 tons/year!

ExxonMobil: DAE has been stopped 2003-12-31(Mobilsol types)

Shell & DEA: DAE has been stopped 2004-06-30(Dealen types, Extrakt IE)

Total/Fina: Step out in 2007

BP: No more business with process oils

DAE will become short

Page 30

DAE Substitutes

Structure DAE TDAE MES RAE NAP

Aromatic > 35 20 - 25 10 - 15 >25 < 10

Naphthenic 30 30 30 30 40

Paraffinic 30 45 60 40 50

Viscosity @ 40 °C 500 - 1.500 200 – 1.200 200 > 3.000 500 - 2.000

VGC 0,96 0,9 0,86 0,87 0,87

VGC = f(Aromatic content, polarity)

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DAE Substitutes

Structure DAE TDAE MES RAE NAP

Aromatic > 35 20 - 25 10 - 15 >25 < 10

Naphthenic 30 30 30 30 40

Paraffinic 30 45 60 40 50

Viscosity @ 40 °C 500 - 1.500 200 – 1.200 200 > 3.000 500 - 2.000

VGC 0,96 0,9 0,86 0,87 0,87

TG - 40 °C - 50 °C - 60 °C -45 - -60 °C - 60 °C

? Availabilityunsure

Available in huge quantities

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Legal Defaults - Consequences

NameStyrene content

[phr]Oil type

Oil content

[phr]

Tg

[°C]

1712 23,5 DAE 37,5 -50

1723 23,5 TDAE 32,5 -52

1732 32,0 MES 32,5 -51

1721 40,0 DAE 37,5 -30

1739 40,0 TDAE 37,5 -36

1740 40,0 MES 32,5 -44

Today also a wide range of label free OE S-SBR is available(for example from Lanxess, DOW, Eni, JSR, Asahi, Nippon Zeon, ..)

Also the first label free OE NR ex Malaysia is available.

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Production of Plasticizers by Extraction

Distillate

PCAs

Aromatics

Paraffins

Waxes

Aromatics

PCAs

DAE

Aromatics

TDAE

MES

Aromatics

Paraffins

Unit DAE TDAE

DMSO-

Extractw-% 25 - 40 < 3

Benzo-(a)-

pyreneppm 30 - 50 < 1

8 Grimmer

substanciesppm 50 - 150 < 10

Page 34

Production of Plasticizers by Hydrogenation

Distillate

PCAs

Aromates

Aliphates

Waxes

MES

Aromates

Aliphates

(more

Alkanes)

NAP

Aromatics

Aliphates

(more

Naphthenes)

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How to chooce the right Oil?

Density: with constant viscosity the density increasesby increasing aromatic content

Viscosity: the viscosity has a drastic impact concerningthe processing behaviours

Both key properties are linked by theconstant of density and viscosity (VGC)

The higher the VGC the higher the aromatic content

VGC =0,755

Density - 0,24 x 0,022 log (viscosity - 35,5)

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BR

NR/IR

SBR

IIR

EPDM

CR

NBR

paraffinic naphthenic aromatic highly syntheticaromatic

0,80 0,85 0,90 0,95 1,00

constant of density and viscosity (VGC)

PVC

DAE

TDAE

MES

NAP

TDAE for new BrIIR:

Optimal results with TDAE

confirmed by Exxon Chemicals(RubberWorld May 2007)

Page 37

� Historical overview

� Plasticizers and Legislation

� Actual Activities

� Conclusion

Page 38

Conclusion

The new legislation is only a problem for the tyreindustry.

That´s not true!

Also the autmotive industry is asking for label freeproducts or products made with uncriticalrawmaterials (Mercedes, GM/Opel, BMW, Toyota).

That means also the TRG producer have to take careof label free plasticizers.

Page 39

Conclusion

The production/purchase of DAE will also becomeproblematic!

• The DAE producers will loose 75 % of the market(tire producers – 20 companies are 95 % of thatmarket)

• 25 % of the DAE market means 25.000 companies• The market becomes uninteresting• DAE will be used more as crackerfeed than as

palsticizer• DAE becomes shorter and expensive

REACHwill this new regulation be the final death of DAE?

Page 40

A last Slide

0

10

20

30

40

50

60

70

80

90

0 10 20 30 40 50

Aromatic content [wt. %]

Vis

co

sit

y@

100 °

C [

mm

²/s]

MES

TDAE

RAE

DAE

PAR

Page 41

Last not least

Do you have any question?

Page 42

Last not least

I wish all of you a merry Christmas and a happy new year!