ELASTOMERE UND KUNSTSTOFFE
ELASTOMERS AND PLASTICS
3-Methyl-thiazolidin-thion-2
MTT
Rheno-
cure MTT
Polylchloropren
Vulcanization
The vulcanization of polychloroprene is
usually performed by using metal oxides
and derivatives of thiourea, mainly ethylene
thiourea (ETU). These vulcanizates are
known to have excellent physical proper-
ties, good aging resistance and very good
sealing properties that are based on the
low compression and tension set. A substi-
tution of ETU is necessary due to its as-
sessment as Potential Carcinogen. Laws or
regulations have already been issued in
several European countries. 3-Methyl-thia-
zolidine-thione-2 (MTT) is an alternative
crosslinking agent for polychloroprene,
which permits an economical and ecologi-
cal optimization of the processing. In the
presence of MTT the amount and the activ-
ity of zinc oxide and magnesium oxide also
show significant influences on the cross-
linking characteristics. This is another way
in which the vulcanization rate can be in-
fluenced. The physical properties, e.g. ten-
sile strength, depend only marginally on the
vulcanization system. Furthermore, signifi-
cant advantages in the compression set
and the aging behavior are found.
Verbesserung der Vernetzung
von Polychloropren
3-Methyl-thiazolidin-thion-2
MTT
Rheno-
cure MTT
Polychloropren
Vulkanisation
Die Vernetzung von Polychloropren wird im
allgemeinen durch Zusatz von Metalloxiden
oder Derivaten des Thioharnstoffs, haupt-
saÈchlich Ethylenthioharnstoff (ETU), durch-
gefuÈhrt. Diese Vulkanisate sind durch sehr
gute physikalische Eigenschaften, eine
gute AlterungsbestaÈndigkeit und sehr gute
Dichteigenschaften durch niedrigen Druck-
und Zugverformungsrest gekennzeichnet.
Ein Ersatz des ETU ist durch die Einstufung
dieses Materials als moÈglicherweise krebs-
erregend erforderlich. Entsprechende Ge-
setze oder Regelungen sind bereits in eini-
gen europaÈischen LaÈndern erlassen wor-
den. 3-Methyl-thiazolidin-thion-2 (MTT) ist
ein alternatives Vernetzungsagens fuÈr Poly-
chloropren, das eine oÈkologische und
oÈkonomische Prozessoptimierung erlaubt.
In Gegenwart von MTT zeigen Typ und
Menge des eingesetzten Zinkoxids und
Magnesiumoxids deutliche EinfluÈsse auf die
Vernetzungscharakteristik. Daraus ergibt
sich eine weitere MoÈglichkeit, die Vernet-
zungscharakteristik zu beeinflussen. Die
physikalischen Eigenschaften des Vulkani-
sats, z. B. die Zugfestigkeit, zeigen nur eine
geringfuÈgige AbhaÈngigkeit vom Vernet-
zungssystem. Ein deutlicher Vorteil zeigt
sich allerdings beim Druckverformungsrest
und der AlterungsbestaÈndigkeit.
KGK Kautschuk Gummi Kunststoffe 53. Jahrgang, Nr. 7-8/2000
Improvement of the Crosslinking
of Polychloroprene1
E. Fuchs, K. S. Reinartz, Leverkusen, (Germany)
Metal oxides and derivatives of thiourea, but that it leads to vulcanizates which
mainly ethylene thiourea (ETU), are nor- show even some superior properties.
mally used to vulcanize polychloroprene
rubber. These vulcanizates are known Experimental
to have excellent physical properties,
good aging resistance and very good For the experiments, a practical usable
sealing properties that are based on the formulation for axle boots was chosen
low compression and tension set. A sub- (Tab. 1a).
stitution of ETU is necessary due to its The standard vulcanization system
assessment as Potential Carcinogen shown in Table 1b was used as a control
[1]. Laws and regulations have already for investigating the different influencing
been issued in several European coun- effects on the MTT-based vulcanization.
tries. ± As polymers, two different grades of
The disadvantage of a thiourea-based polychloroprene were used: a mercap-
vulcanization system is that fine-tuning of tan-modified type (Bayprenâ 110) and
the vulcanization rate is only possible a xanthogen disulfide-modified type
within narrow limits. Usually the reaction (Bayprenâ 116). ± The alternative cross-
rates of crosslinking systems based on linking agents were used in different
ETU are dominated by the vulcanization dosages. These are indicated in the
of the thiourea. Furthermore, a marching described experiments.
modulus can be observed [2]. Standard test methods have been
As alternative crosslinking agent for used to investigate the physical proper-
polychloroprene, 3-methyl-thiazolidine- ties. These test methods are defined
thione-2 (MTT) can be used (Fig. 1). when the results are discussed.
This vulcanization agent provides the
opportunity to adjust the vulcanization
characteristics over a broad range, espe- Tab. 1a. Standard formulation
cially in combination with other commer- Ingredient Level (phr)
cially available crosslinking agents, e. g., CR 100,0
zinc dibenzyl dithiocarbamate (ZBEC). stearic acid 0,5
The scope of the investigations was to ODPA 3,0
evaluate the crosslinking activity of MTT DTPD 3,0
ozone wax 2,5
in comparison to ETU and its influence carbon black N 550 30,0
on the physical properties of the vulcani- carbon black N 774 45,0
zate. It will be demonstrated that MTT is DOS 20,0
aromatic mineral oil 10,0
not only an ecological substitute of ETU
Tab. 1b. Standard crosslinking system
Ingredient Level (phr)
ETU 0,7
TMTD 1,0
standard ZnO 5,0
MgO 4,0
1
Parts of this publication were presented
at a meeting of the American Chemical Society,
Fig. 1. Chemical structure of 3-Methyl-thia- Rubber Division, Nashville, TN, USA,
zolidine-thione-2 (MTT) September 29 ± October 2, 1998.
419
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 Improvement of the Crosslinking of Polychloroprene

Fig. 2. Comparison of the vulcanization rate of ETU and MTT in Fig. 3. Influence of type and dosage of zinc oxide on the vulcaniza-
Baypren 110 tion reaction of ETU and MTT in Baypren 110

Results and discussion
Investigation of the crosslinking
reaction
Besides a direct comparison of vulcani-
zation with ETU and MTT, the influences
of the following factors were investigated:
l dosage of MTT
l type and dosage of zinc oxide
l dosage of magnesium oxide
The vulcanization time of the different
systems was defined on the basis of
the rheometer results (t 90). The experi-
ments were run on a MDR 2000 (Alpha
Technology) at 160 8C (20 min).
To take account of differences in the
thickness of the samples needed for
the performed analytical experiments,
the vulcanization time for each sample
was calculated individually. Internal eval-
uations could show that it is necessary
to prolong the cuing time based on t 90
in order to receive vulcanizates which
show a comparable state of cure. The
additional time depends on the required
samples, e. g. 2 mm thickness for tensile
strength and 6,3 mm for compression
set. The thicker the sample the higher
Tab. 2. Accelerator formulations to investigate the influence of the dosage of MTT
M1 M2
MgO 4 4
standard ZnO 5 5
ETU 0,7 ÿ ÿ
TMTD 1 ÿ
MTT ÿ 0,5
the added time [3]. This procedure leads
to vulcanizates of comparable crosslink-
ing density. Therefore the physical prop-
erties are directly comparable. Further-
more, it is avoided that overcuring or un-
dercuring occurs depending on the rela-
tive crosslinking rate of the individual
samples.
Dosage of MTT
Crosslinking agents were compared
using the combinations given in Tab. 2.
The differing amounts of MTT have
been chosen to evaluate the influence
of the dosage of MTT on the crosslinking
rate. This experiment shows also which
amount of MTT is necessary to substitute
an ETU based system such as the stan-
dard system which has been chosen for
comparison. To investigate the optimum
concentration of MTT a similar experi-
ment has to be performed in the indivi-
dual formulations. In Fig. 2 the vulcaniza-
tion behavior of ETU and MTT are directly
compared in the M-modified CR grade
Baypren 110. It is obvious that MTT
shows a longer onset of cure compared
to ETU. But already at a dosage of
M3 M4 M5
4 4 4
5 5 5
ÿ ÿ
ÿ ÿ ÿ oxide gives a significant increased in
1 2 3 the vulcanization rate. The reduction of
2.0 phr MTT the vulcanization is com-
pleted faster than with ETU.
The results for the XD-modified CR
grade Baypren 116 show a behavior: a
longer onset of the cure reaction and fas-
ter completion of the vulcanization reac-
tion at a dosage level over 1 phr MTT.
This behavior is a clear advantage of
the MTT crosslinking since it gives more
scorch safety in the production process.
Furthermore, there is the opportunity to
reduce cycle times due to the shorter vul-
canization time.
Type and dosage of zinc oxide
To investigate the influence of the zinc
oxide on the vulcanization reaction of
ETU and MTT, the accelerator combina-
tions shown in Tab. 3 were tested.
Fig. 3 shows the influence of the differ-
ent types and amounts of zinc oxide on
the vulcanization rate of the M-modified
CR grade Baypren 110. It is obvious
that the replacement of standard zinc
oxide (here: zinc oxide RS) by a highly dis-
persed zinc oxide grade (here: Zinkoxyd
aktivâ) does not have a significant influ-
ence on the crosslinking of CR with
ETU. It has been described that the influ-
ence of the zinc oxide is less pronounced
in presence of ETU [4].
Completely different behavior can be
observed in the case of MTT vulcaniza-
tion. The replacement of the standard
zinc oxide by a highly dispersed zinc

420 KGK Kautschuk Gummi Kunststoffe 53. Jahrgang, Nr. 7-8/2000

 Improvement of the Crosslinking of Polychloroprene

Tab. 3. Accelerator formulations to investigate the influence of the type and the dosage of behavior but also the influence of the
zinc oxide on the vulcanization reaction of ETU and MTT alternative crosslinking system on the
M1 M6 M3 M7 M8 physical properties.
The accelerator combinations used for
MgO 4 4 4 4 4
standard ZnO 5 ÿ 5 ÿ ÿ these experiments are listed in the tables
ETU 0,7 0,7 ÿ ÿ ÿ above.
TMTD 1 1 ÿ ÿ ÿ Fig. 5a and Fig. 5b show the relation-
MTT ÿ ÿ 1 1 1
highly dispersed ZnO ÿ 5 ÿ 5 2
ship between the tensile strength of the
different test formulations and the
amount of MTT.
Tab. 4. Accelerator formulations to study the effect of magnesium oxide on the vulcani-
zation reaction of ETU and MTT
It is obvious that the tensile strength
increases with increasing amount of
M1 M3 M9 M 10
MTT. This behavior is also illustrated by
MgO 4 4 2 6 the increasing crosslinking density which
standard ZnO 5 5 5 5
is represented by the values of Smax ±
ETU 0,7 ÿ ÿ ÿ
TMTD 1 ÿ ÿ ÿ Smin.
MTT ÿ 1 1 1 The influence of zinc oxide and
magnesium oxide is not very significant.
A slight tendency to a higher tensile
the highly dispersed ZnO from 5 phr to The formulations in Tab. 4 were tested. strength can be observed by using Zink-
2 phr results in a reduction of the cross- The expected effects can be found in the oxyd aktiv or low amounts of magnesium
linking rate to the level of the ETU reaction rheometer data (Fig. 4). oxide. However, these results should not
of the tested formulation. be overestimated since the differences
Similar behavior of the vulcanization re- Investigation of physical are within the range of the test method.
action was observed using the XD-mod- Furthermore, it is important to note that
properties
ified CR grade. In the case of ETU as the compression set can be significantly
crosslinking agent, the change of the The experiments described in this improved by using MTT as crosslinking
zinc oxide grade does not cause any sig- chapter were performed on Baypren agent (Fig. 6a and Fig. 6b).
nificant differences in the reaction rate. 110 but the shown tendencies are also The compression set of those vulcani-
In analogy to the above-described re- found in other CR grades. zates based on MTT is significantly lower
sults, MTT shows a significantly higher compared to ETU-based vulcanizates,
sensitivity to the grade and amount of especially at higher temperatures.
Physical properties of unaged
the zinc oxide. However, in the case of These results show that an MTT-
vulcanizates
the XD-modified CR grade, the addition based crosslinking system leads to
of 2,0 phr highly dispersed zinc oxide It is important to investigate not only the vulcanizates with a significantly improved
leads to a significantly faster vulcanization influence of MTT on the vulcanization sealing force.
but in this case the whole reaction is in-
fluenced. This leads not only to a faster
completion of the reaction but also to a
decrease of the onset of the crosslinking
reaction to the level of ETU. There is still
the advantage of a shorter period of time
to complete the reaction which results in
shorter vulcanization cycles.

Dosage of magnesium oxide

The amount of magnesium oxide is impor-
tant for the vulcanization reaction. By using
smaller amounts of magnesium oxide, the
reaction rate can be increased. This effect
is not only detectable for the onset of cure
but for the complete reaction. On the other
hand, increasing the amount of magne-
sium oxide leads to a slower vulcanization.
As a further influence, it can be observed Fig. 4. Influence of
that the compression set at 100 8C be- magnesium oxide
on the vulcanization
comes slightly worse. reaction of ETU and
MTT in Baypren 110

422 KGK Kautschuk Gummi Kunststoffe 53. Jahrgang, Nr. 7-8/2000

 Improvement of the Crosslinking of Polychloroprene

Fig. 5a. Comparison of the influence of ETU- and MTT-based cross- Fig. 5b. Comparison of the influence of different formulation ingre-
linking density (Smax ± Smin) and tensile strength (acc. to DIN 53504) dients on tensile strength (acc. to DIN 53504)

Fig. 6a. Comparison of the influence of ETU- and MTT-based Fig. 6b. Comparison of the influence of different formulation in-
crosslinking systems on compression set gredients on compression set

Aging behavior in hot air and
oil immersion
Aging processes of vulcanizates depend
not only on the rubber itself but also on
the crosslinking system. Therefore these
properties were investigated using the
compounds listed in Tab. 5. The ex-
periments were carried out using the
M-modified CR grade Baypren 110.
In Fig. 7 the relative change of the ten-
sile strength is shown. It is again shown
that an MTT-based crosslinking system
is advantageous. The change in tensile
strength is significantly smaller compared
to the ETU-based system.
The differing behavior of the test
compounds leads to the conclusion
that the kind of chemical crosslinking
must be different in case of ETU- and
MTT-based crosslinking systems. What
kind of differences are responsible for
these different properties of the vulcani-
zates is yet not clear.
Tear resistance is a very important
physical property for articles that undergo
severe dynamic load during service life.
This property determines the lifetime of
these articles due to its direct correlation
to crack growth.
In this case the tear resistance has
been measured according to DIN 53507.
Fig. 8 shows the initial values for the
unaged compounds. It can be seen
that ETU-based crosslinking systems
give an advantage. However the tear
resistance has always to be seen to-
gether with the influence of aging pro-
cesses. From Fig. 8 it can be seen that
an ETU-based crosslinking system is
much more sensitive to aging than one
based on MTT. After 14 days at 100 8C

KGK Kautschuk Gummi Kunststoffe 53. Jahrgang, Nr. 7-8/2000 423

 Improvement of the Crosslinking of Polychloroprene

Fig. 7. Influence of the crosslinking systems on the change of tensile Fig. 8. Influence of different crosslinking systems on the tear resis-
strength after hot air aging (polymer: Baypren 110) tance after hot air aging (polymer: Baypren 110)

Tab. 5. Crosslinking systems used to evaluate aging processes in vulcanizates (MTT). These experiments are based on
the fact that ETU is a potentially carceno-
M 11 M 12 M 13
genic compound. Its use is already for-
MgO 4 4 4 bidden in several countries.
standard ZnO 5 5 ÿ
ETU 0,7 ÿ ÿ The vulcanization behavior of a mer-
TMTD 1 ÿ ÿ captane modified polychlorprene grade
MTT ÿ 1 1 (here: Baypren 110) and a XD-modified
highly dispersed ZnO ÿ ÿ 2
grade (here: Baypren 116) has been in-
vestigated. The results described in the
following have been detected for both
the relative change of this system is The differences of weight and volume grades in a comparable manner. Basic
significantly stronger compared to MTT- also show advantages for the MTT-based differences in the results are caused by
based systems. The conclusion is that crosslinking system. typical properties of these grades.
the tear resistance of the aged samples It was observed that MTT leads to a
is comparable for the two systems. Summary delayed onset of the cure reaction, which
The oil swelling of MTT-based cross- gives a higher scorch safety, and a
linking systems in IRM 903 is compared The above-described experiments have higher vulcanization rate, which gives
based on the change of the volume been performed to evaluate the possi- the opportunity of shorter vulcanization
and the weight. These results are shown bilities of substituting ethylene thiourea cycles.
in Fig. 9. (ETU) by 3-methyl-thiazolidine-thione-2 Further influence on the vulcanization
reaction can be reached by combining
MTT with zinc oxide grades of higher ac-
tivity. The higher the activity of the zinc
oxide is the faster the crosslinking is.
On the other hand it is possible to use
lower amounts of zinc oxide without
sacrificing the vulcanization rate com-
pared to standard ETU systems.
The amount of magnesium oxide is
also a very important factor which influ-
ences the vulcanization behavior of poly-
chloroprene compounds. The higher the
amount of magnesium oxide is the lower
Fig. 9. Influence of
different crosslink-
the reaction rate is.
ing systems on the Some basic physical properties of
change of weight compounds based on ETU and MTT con-
and volume after taining vulcanization systems have been
oil immersion in
IRM 903 (polymer: determined. It was shown that the com-
Baypren 110) pression set is significantly improved in

424 KGK Kautschuk Gummi Kunststoffe 53. Jahrgang, Nr. 7-8/2000

 Improvement of the Crosslinking of Polychloroprene

delayed in case of the MTT-based vulca-

APPENDIX
Materials Used nization. In addition, the vulcanization is
completed faster compared to ETU.
Description Ingredient Supplier
This opens up the opportunity to reduce
CR Bayprenâ 110 Bayer AG cycle times.
Baypren 116
ODPA Vulkanoxâ OCD
DTPD Vulkanoxâ 3100 Acknowledgements
ozone wax Antiluxâ 110 Rhein Chemie
ETU Rhenogranâ ETU 80 Rhein Chemie The authors want to thank all colleagues who have
MgO Scorchguard 0 Rhein Chemie contributed to this work. Bayer AG's permission to
TMTD Vulkacitâ Thiuram Bayer AG publish the results is acknowledged.
standard ZnO zinc oxide RS Grillo AG
highly disperse ZnO activator Zinkoxyd aktivâ Bayer AG
stearic acid Edenor HT JG-60 Henkel KGaA Literature
carbon black N 550 Corax N 550 Degussa AG
carbon black N 774 Corax N 774 Degussa AG [1] ¹MAK- und BAT-Werteliste 1999ª, Deutsche For-
DOS Witamol 500 Huels AG schungsgemeinschaft, Wiley-VCH, 1999
[2] ªManual for the Rubber Industryº (CD-ROM pub-
aromatic mineral oil Renopal 450 Fuchs MineraloÈlwerke KG
lished by Bayer AG).
[3] Bayer internal report
[4] Technical Information KA-FK-0162 (published by
Bayer AG; available on [2]).
the presence of MTT whereas the other systems based on MTT show significant
physical properties of unaged com- advantages compared to ETU.
Authors
pounds are nearly similar. Also the The experiments described prove that
amount of zinc oxide and magnesium it is possible to replace ETU-based cross- E. Fuchs and K. S. Reinartz work in the Research and
Development Department of the Rubber Business
oxide does not show significant influ- linking systems with MTT. Furthermore, it Group of the Bayer AG.
ences on the general physical properties is possible to vary the crosslinking be-
of the vulcanizate. havior over a broad range. This enables Corresponding author
Dr. Klaus Reinartz
Differences in the physical properties the user to optimize the crosslinking sys- KA-Forschung u. Entwicklung
occur after hot air aging and after oil im- tem to the requirements of the production Spezialelastomere
Bayer AG
mersion. In both cases the vulcanization machinery. Overall, the onset of cure is D-51368 Leverkusen

KGK Kautschuk Gummi Kunststoffe 53. Jahrgang, Nr. 7-8/2000 425