PowerPoint - vkrt 2007-12-13

Plasticizers for the Rubber Industry –
Legislations, Regulations and the
Consequences
VKRT Meeting
2007-12-13
Jürgen Trimbach
Hansen & Rosenthal

Agenda
� Short Introduction of H&R
� Historical overview
� Plasticizers and Legislation
� Actual Activities
� Conclusion
Page 2

Who´s H&R?
H&R WASAG Group
2003 2004 2005 2006
Sales: 211.2m 550m 565m 820m
Chemical/pharmaceutical
raw 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 3

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
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
Page 5

Production and
Tank farm for
Process oils
Tank farm for
Process oils
Blend plant
Sales office
Who´s H&R?
New
projects
Page 6

One short Word
Because of Mrs. Elise Goedhart – van der Hout´s
REACH presentation, Mr. Karl Ehlert´s paper
„Legislation on food contact materials in the
Netherlands, European Union and USA “ and other
lectures I will focus my presentation on Aromatic
Plasticizers.
Page 7

� Historical overview
� Plasticizers and Legislation
� Actual Activities
� Conclusion
Page 8

Approx. 4.000 B. C.
Τεν Τεν λαωσ λαωσ ωερε ενουγη ενουγη
ενουγη
Page 9

Approx. 0
Some 200 laws
concerning
production, trading
and taxes
Page 10

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 11

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.
Page 12

1960
DAE – Distillated Aromatic
Extract - has to be
substituted in printing ink
applications because of ist
carcenoginic potential
Page 13

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 classified
as 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

2007
H&R expands its Hamburg
refinery
– plus 80.000 t noncarcinogenic
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 15

� Historical overview
� Plasticizers and Legislation
� Actual Activities
� Conclusion
Page 16

DIRECTIVE 2005/69/EC
… Furthermore, the tyres
and treads for retreading
manufactured after 1
January 2010 may not be
placed on the market if
they contain extender oils
exceeding the limits
indicated in paragraph 1.
…
Page 17

The Requirements
Plasticizers for tyres have to fullfill:
IP 346 < 3,0 %
B(a)P < 1 ppm or
8 Grimmer PCAs < 10 ppm
BP NMR < 0,35
No exceptions allowed – no aviation, racing or special
industry tyre
Plus
Mutagenicity Index < 1
Page 18

DMSO Extraction (IP 346)
+ Cyclohexane
+ H 2 O/NaCl
Sample +
Cyclohexane, DMSO
+ H 2 O
+ Cyclohexane
Page 19

DMSO Extraction (IP 346)
+ Cyclohexane
+ H 2 O/NaCl
Sample +
Cyclohexane, DMSO
+ H 2 O
+ Cyclohexane
Page 20

Individual PCAs (GC-MS)
Pre-treated sample
Page 21

Individual PCAs (GC-MS)
Page 22

Bay Proton NMR (ISO 21461)
Definition of PCA (= PAH, PNA, PKA, …):
Polycyclic aromatic hydrocarbons are organic compounds
consisting of two or more aromatic rings where certain carbon
atoms are common to two, three or more rings.
The name hydrocarbon indicates that the molecule contains
only carbon and hydrogen.
Page 23

Bay Proton NMR (ISO 21461)
� Extraction with Acetone
� Oil to disolve in CDCl3
� NMR spectrum, calculation
I 2
H Bay = I1 + I 3
x 100
I 1 = Pure Aromatic area
I 2 = Bay region defined from 8,3 ppm to 9,50 ppm
I 3 = Aliphatic and ethylenic regions defined from 0,2 ppm to 5,8 ppm
H = percentage of Bay protons
Page 24

Bay Proton NMR (ISO 21461)
Benzo-(a)-pyrene H
5-Methylchrysene
(not in the Grimmrer substancies)
Bay region
H
H
H
CH 3
H
Bay region
Page 25

Bay Proton NMR (ISO 21461)
Methylnaphthaline
CH 3
Page 26

Bay Proton NMR (ISO 21461)
Methylnaphthaline
Bay region
Benzo-(a)-thiopyrene H
Definition of PCA:
H
H
H
C
Bay region
…. The name hydrocarbon indicates that the
molecule contains only carbon and hydrogen.
H
H
S
Page 27

� Historical overview
� Plasticizers and Legislation
� Actual Activities
� Conclusion
Page 28

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 29

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)
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
TG - 40 °C - 50 °C - 60 °C -45 - -60 °C - 60 °C
Available in
huge quantities
? Availability
unsure
Page 31

Legal Defaults - Consequences
Name
Styrene content
[phr]
Oil type
Oil content Tg
[phr] [°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.
Page 32

Production of Plasticizers by Extraction
Paraffins
Aromatics
MES
DMSO-
Extract
Benzo-(a)pyrene
8 Grimmer
substancies
Waxes
Paraffins
Unit DAE TDAE
w-% 25 - 40 < 3
ppm 30 - 50 < 1
Aromatics
ppm 50 - 150 < 10
PCAs
Distillate
Aromatics
TDAE
DAE
Aromatics
PCAs
Page 33

Production of Plasticizers by Hydrogenation
Aliphates
(more
Alkanes)
Aromates
MES
Waxes
Aliphates
Aromates
PCAs
Distillate
Aliphates
(more
Naphthenes)
Aromatics
NAP
Page 34

How to chooce the right Oil?
Viscosity: the viscosity has a drastic impact concerning
the processing behaviours
Density: with constant viscosity the density increases
by increasing aromatic content
Both key properties are linked by the
constant of density and viscosity (VGC)
VGC =
Density - 0,24 x 0,022 log (viscosity - 35,5)
0,755
The higher the VGC the higher the aromatic content
Page 35

BR
NR/IR
SBR
IIR
EPDM
CR
NBR
PVC
paraffinic naphthenic aromatic highly synthetic
aromatic
TDAE for new BrIIR:
Optimal results with TDAE
MES
NAP
TDAE
DAE
confirmed by Exxon Chemicals
(RubberWorld May 2007)
0,80 0,85 0,90 0,95 1,00
constant of density and viscosity (VGC)
Page 36

� Historical overview
� Plasticizers and Legislation
� Actual Activities
� Conclusion
Page 37

Conclusion
The new legislation is only a problem for the tyre
industry.
That´s not true!
Also the autmotive industry is asking for label free
products or products made with uncritical
rawmaterials (Mercedes, GM/Opel, BMW, Toyota).
That means also the TRG producer have to take care
of label free plasticizers.
Page 38

Conclusion
The production/purchase of DAE will also become
problematic!
• The DAE producers will loose 75 % of the market
(tire producers – 20 companies are 95 % of that
market)
• 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
REACH
will this new regulation be the final death of DAE?
Page 39

A last Slide
Viscosity @ 100 °C [mm²/s]
90
80
70
60
50
40
30
20
10
0
0 10 20 30 40 50
Aromatic content [wt. %]
MES
TDAE
RAE
DAE
PAR
Page 40

Last not least
Do you have any question?
Page 41

Last not least
I wish all of you a merry Christmas
and a happy new year!
Page 42