ROHSTOFFE UND ANWENDUNGEN

RAW MATERIALS AND APPLICATIONS

Process oil
Aromatic extract

Polycyclic aromatic hydrocarbons

Emission
Naphthenic oil
TDAE

MES
DAE
Rolling resistance
Wet
grip
Tire

Safe Process Oils for Tires with

Low Environmental Impact

The global market place is increasingly demanding safe process oils

to reduce the environmental impact
of tires. The replacement of classified distillate aromatic extracts by
non-carcinogenic MES, TDAE, or
naphthenic process oils will reduce
the PAH emissions from tires by
more than 98 %. Rubber tests backto-back with DAE with carbon black
and silica filled vulcanisates show a
slight shift in wet grip performance
and an improvement in rolling resistance for all alternative oils. MES
type oils from different crude oils
and refineries are fully interchangeable in rubber and compound formulations. MES have already been
made on commercial scales in
various parts of the world.

V. Null, Hamburg, Germany

Sichere Prozessole fur

umweltneutrale Reifen
Prozessol
Aromatischer Extrakt

polycyclische aromatische Kohlenwasserstoffe
Emission
Naph l
TDAE
MES
DAE

thenisches O
Rollwiderstand
Nassgriff
Reifen
Die weltweite Nachfrage nach
sicheren Prozeolen wird steigen,
um die Umweltauswirkungen von
Reifen zu verringern. Der Ersatz der
kennzeichnungspflichtigen aromatischen Extrakte durch die nichtkrebserregenden MES, TDAE oder
naphthenischen Prozeole reduziert
die PAH Emissionen von Reifen um
mehr als 98 %. Gummi-Teste im
direkten Vergleich mit DAE an Ruund Silikat-gefullten Vulkanisaten
zeigen eine Verschiebung der Nassrutscheigenschaften und eine
Reduzierung des Rollwiderstands
le. MES O
le
fur alle alternativen O
aus unterschiedlichen Raffinerien
und Roholen sind in Gummi- und
Reifenmischungen vollstandig austauschbar. MES wurde bereits kommerziell in verschiedenen Regionen
der Welt hergestellt.

Distillate aromatic extracts (DAE) are currently used as aromatic process oils for
the manufacture of oil extended natural
or synthetic rubber and also tire compounds. These oils contain high levels
of polycyclic aromatic hydrocarbons
(PAH) and are identified to cause tumours
in various mice skin painting tests [1, 2, 3].
Therefore process oils of the distillate aromatic extract type have consequently
been classified as carcinogenic according to the European legislation (EU Substance Directive 67/548/EEC) and must
be labelled with the risk phrase R 45
(may cause cancer) and the label T
(toxic, skull & crossbones) in Europe [4].
A debate about the environmental impact of aromatic process oils on the emissions from passenger cars tires was initiated by the Swedish Kemi study
(1994), which estimated 14 t/year of polycyclic aromatic hydrocarbons from
10 000 t/year tire wear in Sweden [5]. A
1998 research project sponsored by
the German Umweltbundesamt focused
on the environmental pollution from tire
wear and came to slightly different PAH
estimates. The analysis of individual polycyclic aromatic hydrocarbons from commercial aromatic process oils included
determination of individual carcinogenic
PAHs such as benzo[a]pyrene, benzo[a]anthracene, benzo[b]fluoranthene,
benzo[j]fluoranthene and benzo[k]fluoranthene, and resulted in PAH concentrations between 100 and 1400 mg/kg. This
corresponds to a emission of PAH from
tire wear up to 1.7 t/year for Sweden
[6]. The inconsistency between the two
studies can be explained by the fact
that the authors used different concentrations of polycyclic aromatic hydrocarbons
in aromatic process oils for their calculations [7]. For Germany the Umweltbundesamt study expected the annual
tire wear to grow to 65 000 t/year in

KGK Kautschuk Gummi Kunststoffe 52. Jahrgang, Nr. 12/99

2000, which corresponds to up to 18 t/

year of PAH emissions [6].
PAH emission from tires are significantly higher than those produced from
the exhaust of modern passenger cars.
Volkswagen research published in 1988
showed that the vast majority of PAH
emission was related to passenger cars
diesel engines, with PAH emission rates
of approximately 300 lg/mile [8]. With a
total distance travelled of 530 billion kilometers and a diesel population of approximately 14 %, this corresponded to
a PAH emission of up to 14 t/year for Germany alone. Exhaust PAH emission have
already been significantly reduced by the
introduction of modern diesel engines of
the Euro II type, which cut PAH emission
by more than 95 % [9].
In response to the environmental challenge, the European tire industry trade
group, BLIC (Bureau de Liaison des Industries du Caoutchouc de l'U.E., Brussels) and the IISRP (European Section of
the International Institute of Synthetic
Rubber Producers, London) set up a joint
research programme in co-operation with
the oil industry to identify possible substitutes for distilled aromatic extracts meeting the health, safety and environmental
requirements. The long-term availability
of these safe process oils in sufficient
quantities and from multiple suppliers is
also mandatory, to meet the total demand
of the rubber and tire industry of approximately 200 kt/year for Europe and
800 kt/year on a world-wide basis.
In April 1998 the BLIC/IISRP working
group published in their closing statement that only MES (mildly or medium
extracted solvate) oils meet the mandatory requirements of non-toxicity and
availability at the same time [10]. Treated
distillate aromatic extracts (TDAE) or residual aromatic extracts (TRAE) were also
considered as alternatives but their avail-

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Safe Process Oils for Tires . . .

ability was ranked as not secured in the

volumes required by the European rubber
and tire industry. Untreated residual aromatic extracts do not meet the non-toxicity criterion and were therefore not considered as an acceptable alternative. Hydrotreated naphthenic process oils were
not considered at that time, but they
might be suitable candidates outside
Europe, especially in the USA. It was
also stated that both MES and TDAE
have acceptable processing characteristics in the production of oil-extended
emulsion styrene-butadiene copolymer.
The effect of replacing distillate aromatic
extracts on rubber compound properties
might change compound properties
and some characteristics of rubber and
tire formulations. Therefore development
work to accommodate to the new products in the tire industry might be necessary.
Some European car manufacturers
have already shown strong interest in tires
manufactured with non-labelled oils. In
1998, the German car manufacturers association VDA (Verband Deutscher Automobilhersteller) published a new specification for classified products in car components and parts, which explicitly limits
a maximum of 1 mg/kg benzo[a]pyrene
for extender oils in tires [11].
This article extends the already published studies on the impact of safer process oil types on typical rubber and tire
characteristics [12, 13]. The environmental data of MES, TDAE and naphthenic
process oils were analysed and compared with that for DAE. The process

oils were evaluated in typical tire tread formulations based on carbon black and silica compounds with typical current DAE
as a benchmark.

Manufacturing and availability of

process oils for tire compounds
Distillate aromatic extracts are by-products from the solvent-extraction step
during the refining of standard solvent
neutral lubricating base oils (API Group
I [14]) but contain high concentrations
of polycyclic aromatic hydrocarbons.
The DMSO-extract of a DAE measured
according to IP 346 is typically between
10 and 25 %m [13].
The lubricant market is expected to increasingly demand hydrotreated base
oils (API Group II) for automotive and industrial applications. This will significantly
change the base oil refining structure.
These changes are already taking place
in the US and Far East markets and
Europe is expected to follow [15]. This
trend will reduce the future availability of
DAE, which is used as feedstock for
the manufacture of TDAE.
Treated distillate aromatic extracts
(TDAE) are manufactured from DAE by
further severe processing such as either
hydrotreating or solvent extraction to
meet the threshold of less than 3 %m
DMSO-extract (IP 346 method) to omit
labelling [16]. The manufacture of TDAE
via the solvent extraction route has
been protected by patents [17, 18].
DAE is used as cat cracker feed in
most refineries and the processing to

TDAE might require substantial capital investments where suitable hardware is not
available.
MES and the severely processed
naphthenic process oils (NAP) are
made from the corresponding paraffinic
or naphthenic distillates, either via solvent
extraction or hydrotreating. MES type
products have already been manufactured on a commercial scale at different
refineries and are available world-wide,
e. g. as Shell Catenex SNR. The availability of naphthenic process oils is
much higher in the USA than in Europe.
These oils are already commercially available, e. g. outside USA as Shell Gravex
181 or in USA as Shellflex 794 respectively [12, 13]. The PCA contents of these
oils are carefully controlled to stay below
the 3 %m threshold of the EU Substance
Directive and hence not classified and
free of labelling constraints [19].

Solvency characteristics of noncarcinogenic process oils

The physical and chemical properties of
two MES, one TDAE, one NAP and a typical DAE as a benchmark are summarised in Table 1. Two MES type process oils were manufactured from different feedstocks in different refineries via
the solvent extraction (MES 2) or the hydrotreatment (MES 1) route. NAP represents a hydrotreated naphthenic process
oil from the USA. TDAE is a non commercial research product.
The solvency characteristic of these
process oils is best described by the

Table 1: Characteristic data of process oils

Process Oil
Colour
Density at 15 8C, kg/m3
Refractive index at 20 8C
Flash point COC, 8C
Pour point, 8C
Kin viscosity at 40 8C, mm2/s
Kin viscosity at 100 8C, mm2/s
Viscosity gravity constant (VGC)
Carbon type distribution CA/CN/CP
(non S-corr.), %
Sulphur, %m
Aniline point, 8C
Clay gel analysis, %m
polars/aromatics/saturates
PCA content (DMSO), %m
Glass transition point (Tg), 8C

800

DAE

TDAE

NAP

MES 1

MES 2

DIN ISO 2049

DIN 51757
DIN 51423-2
DIN ISO 2592
DIN ISO 3016
DIN 51562-1
DIN 51562-1
DIN 51378
DIN 51378

D8.0
1002
1.570
260
30
1500
31
0.957
41/31/28

D8.0
939
1.520
264
27
210
14.5
0.880
19/23/58

5.5
938
1.512
252
15
785
25.0
0.863
11/43/46

2.0
909
1.501
266
15
175
14.2
0.840
12/30/58

7.0
914
1.504
250
6
179
14.4
0.846
13/31/56

DIN ISO 2977

ASTM D 2007

4
50
10/70/20

2.8
74
2/43/55

1.0
85
2/51/47

0.4
99
1/42/57

1.4
95
1/50/49

IP 346
Bayer ELA 601

20
43

1.3
58

1.2
43

1.4
64

1.1
66

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Safe Process Oils for Tires . . .

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801

Safe Process Oils for Tires . . .

viscosity gravity constant (VGC) and the

aniline point. With VGC values of the
two MES oils relatively close at around
0.845, the solvency characteristics for
NAP (VGC 0.863) and TDAE (VGC
0.880) are expected to slightly improve.
The aniline points of these oils rank the
solvency power in the same order. As expected, the aromatic process oil DAE has
the lowest aniline point and the highest
VGC, which indicates the best solvency
properties. This difference between DAE
and all non-carcinogenic process oils appears to be significant. TDAE has the best
solvency characteristic and is closely followed by NAP and MES.

Reduced PAH emissions with

safe process oils
The concentrations of toxic and hazardous polycyclic aromatic hydrocarbons
(PAH) were used to indicate the environmental impact of process oils. Some
polycyclic aromatic hydrocarbons (PAH)
with benzo[a]pyrene as the leading compound are known to cause skin cancer in
animals [1, 2, 3]. The DAE, TDAE 2, NAP
and MES process oils were analysed for
more than 20 individual compounds of
the PAH type and the results are reported
in Table 2. It is possible to calculate different sums from the list, e. g. the so-called
sum of Grimmer-PAH which includes the
16 Grimmer selected PAH [20].
As expected, the distillate aromatic extract contains high concentrations of carcinogenic PAH. The sum of total PAH was
determined as 443 mg/kg and the sum of
Grimmer-PAH as 280 mg/kg. Benzo[a]pyrene was found at 12 mg/kg, well
above the limit of 1 mg/kg set by the
VDA for process oils in tires. PAH analysis
of the non-carcinogenic process oils
shows significantly lower concentrations
of carcinogenic PAH in each case. The
sum of total PAH was in a range from 2
to 6 mg/kg, the sum of Grimmer-PAH
was in the range from 1 to 5 mg/kg
and benzo[a]pyrene as leading compound was a maximum of 0.2 mg/kg.
All non-carcinogenic process oils meet
the VDA limit for benzo[a]pyrene.
Severe processing steps which are required to meet the 3 %m threshold for the
DMSO-extract also result in low PAH
concentrations. Distillate aromatic extracts contain approximately 100 times
higher PAH concentrations if compared

802

Table 2: Individual polycyclic aromatic hydrocarbons (PAH) in process oils

Individual PAH [mg/kg]

Grimmer DAE

Fluoranthene
Pyrene
Benzo[a]fluorene
Benzo[b c]fluorene
Benzo[b]naphtho[2,1-d]thiophene
Benzo[g]fluoranthene, -[h]-, -[i]Benzo[a]anthracene
Chrysene Triphenylene
1 2 3 4 5 6-Methylchrysenes
Benzo[b j k]fluoranthen
Benzo[e]pyrene
Benzo[a]pyrene
Perylene
Dibenz[aj]anthracene
Indeno[1,2,3-c,d]pyrene
Dibenz[a,h]anthracene, -[a,c]Benzo[b]chrysene
Dibenzo[g,h,i]perylene
Anthanthrene
Coronene
Total sum of PAH
Sum of Grimmer PAH (x)

x
x

x
x
x
x

x
x
x

x
x
x
x
x

Compounding
The influence of different process oil
types in the rubber mixtures has been
tested in a series of experimental tire
tread compounds based on typical carbon black and silica formulations backto-back with DAE. The full recipes are
shown in Tables 3 and 4.
Table 3: Carbon black compound

NAP

MES 1

MES 2

1
7
26
15
15
6
6
48
73

< 0.1
0.1
0.1
0.3
0.1
0.4
0.1
0.1
0.4
0.1
< 0.1
< 0.1
< 0.1
0.1
0.2
0.4
0.4
1.7

< 0.1
< 0.1
< 0.1
< 0.1
< 0.1
< 0.1
< 0.1
0.2
0.9

0.1
0.3
0.2
< 0.1
0.3
0.1
0.1
< 0.1
0.3

64
45
12
49
1
8
8

0.1
0.1
< 0.1
< 0.1
< 0.1
< 0.1
< 0.1
0.1
< 0.1
< 0.1
< 0.1
2
1

< 0.1
0.5
0.2
0.3
< 0.1
< 0.1
0.5
< 0.1
0.8
< 0.1
2.8
6
5

< 0.1
0.1
0.1
< 0.1
< 0.1
< 0.1
< 0.1
0.1
< 0.1
< 0.1
< 0.1
2
1

49
6
4
443
279

to all non-carcinogenic process oils. Replacing DAE by non-carcinogenic process oils will reduce the PAH emissions
from tires by more than 98 %.

TDAE

0.3
0.4
0.2
0.4
< 0.1
< 0.1
< 0.1
0.1
0.2
< 0.1
0.1
5
2

Non-oil-extended ESBR 1712 with NR

and BR (50/25/25) was the polymer base
for the carbon black compound. For the
silica compounds a non-oil-extended
SSBR (25 % styrene, 50 % vinyl-butadiene) with BR (70/30) was used. Commercial DAE was used as a reference
and MES 1 was also from commercial
production. Rubber formulating, compounding and testing were carried out
at Bayer AG, Rubber Business Group,
Leverkusen, Germany.

Table 4: Silica compound

Component

phr

Component

phr

E-SBR, oil-free (Krynol 1712)

BR (Buna CB 25)
NR (TSR 5, Defo 700)
Process oil
Carbon black N 234
Zinkoxide
Stearic acid
Vulkanox 4020
Vulkanox HS
Light stability agent (Antilux 654)
Vulkacit CZ
Vulkacit D
Sulphur

50
25
25
37,5
55
3
1,5
1
1
1
1,6
0,3
1,6

SSBR (Buna VSL 5025-0)

BR (Buna CB 25)
Process oil
Carbon black N 121
Silica (Vulkasil S)
Silane Si69
Zinkoxide
Stearic acid
Vulkanox 4020/HS
Light stability agent (Antilux 654)
Vulkacit CZ
Vulkacit D
Sulphur

70
30
37,5
10
70
5,6
3
1
2
1
1,4
2,0
1,6

KGK Kautschuk Gummi Kunststoffe 52. Jahrgang, Nr. 12/99

Safe Process Oils for Tires . . .

Compound properties
The experimental carbon black and silica
compounds were vulcanised and analysed for Mooney viscosity, scorch time
TS3/130 8C, t90 (170 8C) and delta torque (S'max S'min). The data are shown
as standardised spider diagrams with the
results of the DAE compound set as 100
(Figure 1). Results greater than 100 indicate a better performance, results lower
than 100 indicate a poorer performance.
Overall no drastic differences have
been observed during vulcanisation of
the carbon black or the silica filled compounds. The compound Mooney viscosity decrease more by the use of MES oil. A
possibly improved compatibility of DAE
with styrene butadiene rubbers might
cause a reduction of the delta torque
(S'max S'min) during vulcanisation.

Vulcanisate properties
The impact of the different process oils on
the performance in finished tires was
evaluated in selected laboratory tests.
All results are summarised in Figure 2
as separate spider diagrams each for carbon black and silica vulcanisates with
DAE as reference. Results greater than
100 indicate a better performance and results less than 100 indicate a poorer performance. No significant impact of the
process oils was observed on properties
such as tensile strength, elongation,
modulus and hardness for both the carbon black and the silica filled vulcanisates. For the carbon black filled vulcanisates the tear resistance for all safe process oils was lower compared to that of
DAE. For the silica filled vulcanisates the
differences in tear resistance were only
marginal with NAP and TDAE showing
a slight improvement and MES slightly
poorer results. A significant improvement
for all safe process oils was observed in
DIN abrasion tests for both vulcanisate
types. Overall, the effects of the oil types
were more significant for the carbon
black filled compound, which presumably may caused by different interactions
between the carbon black or silica filler
and the process oils.
Modern passenger car tires are expected to perform best in wet grip handling to guarantee high driving safety
and to reduce fuel consumption. The
damping characteristics at 0 8C are

Figure 1: Effect of process oil type on compound properties of carbon black and silica compounds (data standardised, DAE reference 100, greater than 100: better, lower than 100:
worse)

used to indicate the wet grip performance. Low rolling resistance, indicated
by the tan d at 60 8C value is directly
correlated to low fuel consumption. The
tan d curves were analysed at a frequency
of 10 Hz (Roehlig) and the tan d versus
temperature curves are shown in Figure 3
for carbon black and in Figure 4 for silica
filled vulcanisates over the temperature
range from 30 to 70 8C.
At higher temperatures, the tan d for all
safe process oils are on a comparable
level and significantly lower than the
tan d for DAE. At lower temperatures, a
different behaviour was observed be-

tween the carbon black and silica filled

vulcanisates. For the carbon black filled
vulcanisates, DAE showed the highest
tan d between 10 and 10 8C, NAP
and TDAE being comparable and intermediate and MES shows slightly lower
values. For the silica filled vulcanisates
in the range from 5 to 10 8C the tan d
for DAE and NAP were on a comparable
level and the tan d for TDAE and MES
were found below. At 0 8C NAP showed
a higher tan d than DAE followed by TDAE
and MES. At 10 8C the tan d for all safe
process oils were at the same level and
significantly higher than that of DAE.

Figure 2: Effect of process oil type on vulcanised properties of carbon black and silica compounds (data standardised, DAE reference 100, greater than 100: better, lower than 100:
worse)

KGK Kautschuk Gummi Kunststoffe 52. Jahrgang, Nr. 12/99

803

Safe Process Oils for Tires . . .

Figure 3: Effect of process oil type on tan d versus temperature

curve of carbon black filled vulcanisates

A 1:1 substitution of DAE by safe process oils in typical tire tread formulations
based on E-SBR with carbon black and
S-SBR with silica results in some
changes in rubber performance for all
types of alternative oils when compared
with DAE. The tan d 60 8C was at a comparable level for all oils and significantly
below DAE. This was expected from
the lower glass transition points (Tg) of
the oils resulting in lower tan d at higher
temperatures for the corresponding vulcanisates. This observation is also in
line with the reduced heat built up during
vulcanisation. The wet grip performance
indicated by the tan d 0 8C is slightly
poorer for MES and TDAE. With some
modifications in tire formulations the expected wet grip and wet brake performance can also be met with non-carcinogenic oils.
The evaluation of different MES type
oils made to the same specification
from different refineries and different
crude oils shows no differences during
vulcanisation or in the finished tread compounds. This proves the full interchangeability of MES in rubber and tire formulations.

Conclusion
The environmental impact and the performance in typical tire tread formulations of
medium extracted solvates (MES) from
different refineries, a naphthenic process
oil (NAP) and a treated distillate aromatic
extract (TDAE) have been evaluated
back-to-back with DAE.

804

Figure 4: Effect of process oil type on tan d versus temperature

curve of silica filled vulcanisates

All non-carcinogenic process oils contain very low concentrations of polycyclic

aromatic hydrocarbons and meet the
1 mg/kg benzo[a]pyrene limit set by the
VDA. Hence, the replacement of DAE
by non-carcinogenic process oils in oilextended natural or synthetic rubber
and therefore in finished tires will reduce
the PAH emission from tire wear by more
than 98 %.
Rubber testing of vulcanisates indicated an improvement of rolling resistance for all non-carcinogenic oils, especially in carbon black compounds. NAP
and TDAE performed slightly better in
the damping test at low temperatures if
compared to MES. The different MES
oils made in different refineries from different crude oils show very similar performance in the rubber testing, indicating
their full interchangeability in tire tread formulations. The differences between
TDAE and MES are only marginal in the
reported rubber tests, and it can be expected that a small adaptation of the
tire formulations will allow the use of
MES oils even in those applications
where TDAE appears to be more favourable.
The ongoing global changes in refinery
designs to meet the future demand for
Group II/III lubricating base oils will reduce
the long-term availability of TDAE and its
feedstock. MES can easily be made available in almost every lubricant plant via established and available refining processes. It has already been demonstrated on commercial scales that MES
can be made in different parts of the
world.

These test results are intended to support the rubber and tire industries in their
environmental challenge to replace the
classified aromatic oils. Further extensive
compounding and evaluation work will be
required by each company using its proprietary tire formulation technology. Demand for these oils is expected to rise
as car manufacturers realise that carcinogenic emissions from tires can hereby be
greatly reduced. It has already been demonstrated on a commercial scale that
this challenge can be met by a change
to safer alternatives such as MES. The
production of Shell Catenex SNR began in 1997 and the first tires with this
safe oil are already on the market.
Acknowledgement
The author would like to thank Jurgen
Trimbach, Bayer AG, Leverkusen, for
his excellent cooperation, extensive evaluations and discussions.

References
[1] International Agency for Research on Cancer
Monographs Evaluation of Carcinogenic
Risk. Vol. 32, Lyon, France (1983).
[2] International Agency for Research on Cancer:
Mineral oils. In: IARC Monographs on the Evaluation of the Carcinogenic Risk of Chemicals
to Humans Vol. 33, Lyon, France, April (1984)
148.
[3] S.M.A. Doak et al., Br. J. Cancer 48 (1983) 429.
[4] Commission Directive 93/72/EEC of 1 September 1993, 19th ATP of Council Directive 67/548/
EEC, O.J. L258 (1993) 29.
[5] U. Duus, J. Ahlbom, I. Anderson, Toxic oil in
rubber tires, KEMI National Chemicals Inspectorate, 6 (1994), Solna.
[6] W. Baumann, M. Ismeier, Kautsch. Gummi,
Kunstst. 51 (1998) 182.

KGK Kautschuk Gummi Kunststoffe 52. Jahrgang, Nr. 12/99

Safe Process Oils for Tires . . .

[7] H. Schnecko, Kautsch. Gummi, Kunstst. 48

(1995) 237.
[8] H. Klingenberg et al., Nicht limitierte AutomobilAbgaskomponenten, Volkswagen AG, Forschung und Entwicklung 1988.
[9] P. Kohoutek; J. Beyersdorf et al., Wiener Motorensymposium Mai 1998, VDI-Forschungsberichte, VDI-Reihe 12: Verkehrstechnik, Fahrzeugtechnik 1998.
[10] BLIC/IISRP Working Group Closing Statement,
21/04/1998, Brussels.
[11] Verband der Automobilindustrie e. V. (VDA), VDA
232-101; 1998, Frankfurt.
[12] J. Pocklington, Tire Technology International
(1998) 43.

[13] V. Null, Tire Technology International (1999) 21.

[14] API Publication 1509 14th Edition, American
Petroleum Institute.
[15] M.Lemmon et.al., National Petroleum Refiners
Association annual meeting, San Antonio (US),
16 18 March 1997.
[16] CONCAWE Report 94/51.
[17] European Patent 0417980A1 (Priority date:
12.09.1989).
[18 European Patent EP 0839891 A2 (Priority date:
31.10.1996).
[19] Commission Directive 94/69/EC of 19 December 1994, 21th ATP of Council Directive 67/
548/EEC, O.J. L381 (1994) 1.
[20] Grimmer, G., Jacob, J. und Naujack, K.W., Fresenius Z. Anal. Chem. 306 (1981) 347.

KGK Kautschuk Gummi Kunststoffe 52. Jahrgang, Nr. 12/99

The author
Dr. V. Null works at Shell Global Solutions as Technology Manager for Industrial Specialities
Correspondence
Dr. V. Null, Shell Research and Technology Centre
Hamburg, PAE Labor, Hohe-Schaar-Strae 36
21107 Hamburg, Germany

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