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
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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
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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?
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
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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.
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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
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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.
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� Historical overview
� Plasticizers and Legislation
� Actual Activities
� Conclusion
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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
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DMSO Extraction (IP 346)
Sample + Cyclohexane, DMSO
+ Cyclohexane+ H2O/NaCl
+ H2O
+ Cyclohexane
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Individual PCAs (GC-MS)
Pre-treated sample
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Individual PCAs (GC-MS)
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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.
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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
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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
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Bay Proton NMR (ISO 21461)
CH3
Methylnaphthaline
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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.
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� 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
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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
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
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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)
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� 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.
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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?
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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
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Last not least
Do you have any question?
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Last not least
I wish all of you a merry Christmas and a happy new year!