ROHSTOFFE UND ANWENDUNGEN
RAW MATERIALS AND APPLICATIONS
Crosslinked rubber
Recycle
Automo-
tive rubber waste
Devulcanization

Reclaimed rubber
Thermoplastic elas-
tomer
A new recycling technology for cross-
linked rubber was developed using con-
tinuous reactive processing methods. In
the process of producing reclaimed rub-
ber, a breakage of crosslinking points in
the rubber matrix occurs selectively un-
der optimized controls of shear stress,
reaction temperature and internal pres-
sure in a twin screw extruder corre-
sponding to the dynamic devulcanization
process. The reclaimed rubbers show
excellent mechanical properties applic-
able to new rubber compounds.
Furthermore, an enhanced rubber recy-
cling process including both the dynamic
devulcanization and dynamic vulcaniza-
tion for producing thermoplastic elasto-
mer (TPE) based on rubber waste has
been established. The obtained TPE ex-
hibits a highly recoverable rubber elas-
ticity and mechanical properties com-
parable to commercial TPE.
Dynamische Devulkanisation
und dynamische Vulkanisation
zur Wiederverwertung von ver-
netzten Kautschuken
Vernetzter Kautschuk
Wiederverwer-
tung
Automobilgummiabfälle
De-
vulkanisation
regenerierter Kautschuk

thermoplastische Elastomere
Eine neue Recyclingtechnologie für ver-
netzten Kautschuk auf der Basis eines
kontinuierlichen reaktiven Verfahrens im
Zweischneckenextruder wurde entwick-
elt. In dem Prozess wird Regenerat durch
die selektive Aufspaltung von Vernet-
zungsstellen in der Kautschukmatrix in
einem Scherfeld und unter Einwirkung
von Druck und Temperatur hergestellt.
Das Regenerat zeigt ausgezeichnete
mechanische Eigenschaften im Vergleich
zu neuen Compounds. Weiterhin wurde
die dynamische Devulkanisation von
Altgummi zur Herstellung von TPV in
einem dynamischen Vulkanisationspro-
zess eingesetzt. Die erhaltenen TPV zei-
gen eine hohe Elastizität und mechan-
ische Eigenschaften die den kommerziell
erhältlichen TPV vergleichbar sind.
Dynamic Devulcanization and
Dynamic Vulcanization for Re-
cycling of Crosslinked Rubber1)
Recently recycling of waste materials is
growing importance for all the industries
in the world. The automotive and transpor-
tation industries are the biggest consumers
of raw rubber. Rubber waste is usually gen-
erated from manufacturing products during
the process and by the post-consumer (re-
tired) products, mainly including scrap tires.
In Japan about one million tons of scrap
tires are generated annually, to example.
From the point of energy balances a mate-
rial recycling of rubber waste is preferable
to any other recycling techniques [1]. How-
ever, the material recycling in form of
crumb rubber and reclaimed rubber results
in only about 11.5 % of the whole scrap tires
in 2004 [2]. The oldest and simplest reclaim-
ing method in the rubber recycling industry
is called ‘‘pan method”. The reclaimed rub-
ber obtained by this method is much infer-
ior in physical properties to the virgin (new)
rubber. Technological developments for the
tires such as steel belted and radial ones
cause some limitation to the amount of re-
cycled rubber in higher quality rubber com-
pounds for new tires [1]. Hence, new mate-
rial recycling technologies such as micro-
wave method [3] and ultrasonic method
[4] have been developed for the aim of
shorter reaction times. However, the re-
claimed rubbers obtained by these methods
are not quite excellent in quality as to be
widely applicable in practical rubber pro-
ducts.
In this study a new continuous rubber recy-
cling technology has been developed for
crosslinked rubber for the purpose of ob-
taining recycled materials in high quality
as reclaimed raw rubber and thermoplastic
elastomer (TPE) based on rubber waste.
Rubber recycling technology
Automotive rubber waste
For motor vehicles many crosslinked rubber
products are used as weather strips, hoses,
vibration insulators and miscellaneous
parts except tires as shown in Figure 1 [5].
The sum of their weights is corresponding
to about 3 % of the total weight of the ve-
hicle. Among rubbery polymers for these
automotive rubber products, the use of
ethylene-propylene-diene rubber (EPDM)
amounts to be about one half of them by
weight as shown in Figure 1. In this study
a continuous rubber recycling technology
has been developed mainly for crosslinked
EPDM waste.
Recycling process of producing
reclaimed rubber
Principle of producing reclaimed rubber
Material recycling of crosslinked polymers
including rubber is generally thought of
as being a difficult by using simple heating
procedure, because of the three-dimen-
sional network structure restricting the ma-
terial from melting. In the rubber recycling
process using the conventional the pan
method, finely ground rubber powder
mixed with oils and reagents is heated
with steam in the pressure vessel at the
temperature of  200 C for more than 5
hours. Moreover, this process usually has
to be followed by several procedures (refin-
ing and straining) for obtaining the final re-
Autoren
K. Fukumori, M. Matsushita,
M. Mouri, H. Okamoto, N. Sato,
K. Takeuchi and Y. Suzuki,
Aichi (Japan)
Corresponding author:
Dr. Kenzo Fukumori
Toyota Central
R & D Labs. Inc
Nagakute
Aichi, 480-1192, Japan
Tel. + 81/5 61 63-52 51
Fax: + 81/5 61 63-64 98
E-mail: fukumori-k@mosk.tytlabs.co.jp
1
This paper was partly presented at IRC 2005
YOKOHAMA, Oct. 24 – 25, 2005.
KGK
Juli/August 2006 405
Discover more interesting articles
and news on the subject!

www.kgk-rubberpoint.de

Entdecken Sie weitere interessante

Artikel und News zum Thema!
 ROHSTOFFE UND ANWENDUNGEN
RAW MATERIALS AND APPLICATIONS
&
1 &
&
2 &
&
3 &
&
4 &
claimed rubber. The reclaimed rubber ob-
tained by this method is much inferior in
physical properties to a new rubber, due
to the occurrence of the breakages of
both the crosslinking points and main chain
(C-C) bonds unselectively.
406 KGK
Juli/August 2006
as the shear stress, the temperature and
1 Rubber products
the internal pressure. This dynamic devulca-
for motor vehicles
nization process for crosslinked rubber
waste is performed on a modular screw
type reactor (i.e., twin screw extruder) as
schematically shown in Figure 2. For this
equipment, the screw configuration with
the modular screw elements (right-handed
screw, kneading disk, etc.) is suitably de-
signed to be applicable to the dynamic de-
vulcanization process. The rubber waste
was roughly crashed into small pieces in
the size of about 5 mm for the following re-
cycling process. In the first pulverization
2 Schematic illus- zone of this process roughly crashed rubber
tration of the re- material becomes into fine particles by high
actor for the dy-
shearing, and heated to the devulcanization
namic devulcani-
zation reaction temperature quickly. The residence
time is assured to be enough to complete
the devulcanization reaction under a shear
flow in the next devulcanization zone. In
this reaction zone, fine particles of cross-
linked rubber become highly elongated by
filling and shearing with the kneading
disk elements, as well as being plasticized
eventually.
A basic understanding for the cleavages of
3 Breakages of
crosslinking crosslinking bonds under high shear stress
points in high is suggested as following. As shown in Fig-
shear flow: (a) ure 3 there appears to be a small difference
model for the in the bonding energy between C-C bonds
network chain; and C-S or S-S bonds. Hence by simple heat-
(b) deformation
ing in the pressure vessel, the cleavages of
of the network
chain (particu- both the C-C and C-S or S-S bonds may occur
larly, S-S- bonds) unselectively. This causes the lowering of
by shearing the physical properties for reclaimed rubber
by the conventional method. On the other
hand, with regard to the elastic constant
4 Dynamic devulca- k for these bonds (approximately estimated
nization process on the basis of the values for crystals), the k-
for the product of value for the S-S bonds can be estimated to
reclaimed rubber be about 1/30th of the one for the C-C
bonds as shown in Figure 3a. Generally, it
is understood that mechanical behavior of
crosslinked rubber may be mainly con-
trolled by the entropic term in the strain en-
ergy. In the contrast with this entropic de-
formation behavior at extremely higher
shear stress induced by filling and kneading
in the reactor, most of the rubbery mole-
cules may become to be fully elongated
to their limited extensibility. Under these
conditions, the spring having a lower elastic
constant (the S-S bonds) may become more
extended as compared with the spring hav-
In the newly developed continuous recy- ing a higher elastic constant (the C-C bonds)
cling process [6], various chemical reactions in an elastic manner as shown in the Figur-
corresponding to the selective breakage, of e 3b. The elastic energy induced by high
crosslinking points (so-called, devulcaniza- shearing may be particularly concentrated
tion) can be efficiently controlled by opti- at the S-S bonds causing the breakages of
mizing the parameters in the reactor such crosslinking points selectively.
 of the screw. As for the materials sampled
&
5
from various positions, the Mooney viscos-
ity, the fractions of the sol and gel compo-
nents, the molecular weight distribution for
the sol component and the effective net-
work chain density for the gel component
were evaluated. Furthermore in this study,
the change in the crosslink structure for
these materials were analyzed with the che-
micals such as thiol/amine reagents, which
are used to cleave sulfur bonds. A mixture
of propane-2-thiol and piperidine in hep-
tane is used to cleave polysulfide bonds,
and with hexane-1-thiol in piperidine, poly-
sulfide and disulfide bonds can be cleaved
[6]). According to this procedure a full char-
acterization of partially decrosslinked net-
work structure during the dynamic devulca-
&
5 Appearances and Mooney viscosity of rubbers sampled from the positions A – E nization processing can be investigated.
Under suitable process conditions (i.e.,
&
6 &
6 Spatial heteroge- screw configuration, reaction temperature,
neity in structure screw rotation speed, etc.) for EPDM, the re-
of reclaimed rub- claimed EPDM in good surface appearance
ber by devulcani- can be continuously obtained from the
zation
head of the reactor as shown in Figure [4].
This behavior was closely connected with
the appropriate values of the Mooney visc-
osity for the reclaimed EPDM according to
the rubbery polymer. Figure 5 shows the
changes in the appearance and Mooney
viscosity of the EPDM sampled from the var-
ious positions along the axial length of the
screw in the reactor. In the first pulveriza-
tion zone, roughly crashed rubber material
is turned into fine particles by high shear-
ing. In the next devulcanization zone, the
fine particles of the crosslinked EPDM be-
&
7 &
7 Changes in the
average molecu- come to be plasticized. The Mooney viscos-
lar weight of sol ity of the EPDM samples decreases along
component in the axial length of the screw, corresponding
rubbers sampled to the progress of the devulcanization.
from positions The reclaimed EPDM obtained by devulcani-
A–E
zation is composed of the sol (the fraction
soluble in toluene) and gel (the insoluble
fraction) components. As for the reclaimed
EPDM under typical devulcanization condi-
tions, the fractions of the sol and gel com-
ponents were evaluated to be about 44 %
and 56 %, respectively. Furthermore, the ef-
fective network chain density for the gel
component was evaluated to be 1/20th
of the originally vulcanized rubber. Figure 6
shows schematically the spatial heteroge-
neity in the reclaimed rubber, for which
there appears to be mixtures of uncros-
slinked polymer chains assigned to the sol
component and loosely crosslinked ones as-
Change in the network structure during under a typical test condition were studied signed to the gel component. Figure 7
the dynamic devulcanization process by pulling out the screw quickly from the shows the changes in the average molecu-
The temporal changes in the rubber matrix barrel of the reactor on the way and sam- lar weight of the sol component during the
during the dynamic devulcanization process pling the materials along the axial length process. The average molecular weight of

KGK
Juli/August 2006 407

 ROHSTOFFE UND ANWENDUNGEN
RAW MATERIALS AND APPLICATIONS

stage of the process, the numbers of the

&
8 &
8 Changes in net-
di- and polysulfidic bonds decrease, while
work structure
during the dy- the number of the monosulfidic bonds in-
namic devulcani- creases. At the late stage of the process
zation process: the number of the monosulfide bonds de-
the numbers of creases, and finaly becomes to be negligibly
mono-, di- and small. On the other hand, only by heating in
polysulfide bonds a pressure vessel with flowing nitrogen gas,
the number of the poly- and disulfidic
bonds decrease, but the number of the
monosulfidic bonds increases. During the
dynamic devulcanization process in the re-
actor, the di- and polysulfide bonds are
firstly converted into the form of the mono-
sulfidic bonds, and then the monosulfidic
bonds finally may come to be cleaved under
high shear stress and internal pressure.
&
9
Deodorization of reclaimed rubber
The characteristic odor from reclaimed rub-
ber may cause the limits to its practical ap-
plications. Hence, a deodorization proce-
dure for reclaimed rubber is also included
in the dynamic devulcanization process by
a newly developed method [7], in which
high-pressured water is injected into a bar-
rel.
The deodorization mechanism during the
dynamic devulcanization process is schema-
tically shown in Figure 9a: odorous compo-
nents in the rubber compound come to be
trapped into the high-pressured water va-
&
9 Deodorization during the dynamic devulcanization: (a) deodorization mechanism
(b) signals from odorous components in rubbers por and removed efficiently through vents
with vacuum pumps. The barrel tempera-
ture and screw elements around the posi-
&
10 &
10 Stress-strain
tions for the water injection are suitably ad-
curves of cross-
linked rubbers justed to avoid an inadequate progress of
the devulcanization caused by the de-
creased temperature through the diffusion
of water molecules. Figure 9b shows the
GC-peaks of the odorous components in re-
claimed rubbers (both untreated and trea-
ted) and new rubber compound. For the re-
claimed rubber, the odorous components in
the treated rubber are hardly detected simi-
lar to those in the new rubber compound
while there are many odorous components
detected in the untreated rubber.

Properties of reclaimed rubber and its

the sol component in the reclaimed EPDM is
nearly constant, comparable to the one in
new EPDM, from the position B to the posi-
tion D. This result supports the occurrence
of selective breakages of crosslinking points
in the EPDM during the dynamic devulcani-
zation process.
Figure 8 shows the changes in the the
amounts of the mono-, di- and polysulfidic
bonds in the network structure during the
process. Initially, for the crosslinked rubber,
the fraction of mono-, di- and polysulfide
bonds were evaluated to be about 20 %,
20 % and 60 %, respectively. In the early
practical uses for automotive rubber
products
The reclaimed EPDM can be compounded
and crosslinked with accelerated sulfur vul-
canization system according to the conven-
tional recipe. Figure 10 shows typical stress-
strain curves of crosslinked rubbers for the
reclaimed EPDM by the developed method
and new rubber. The reclaimed EPDM exhi-
bits excellent tensile stress-strain property
almost comparable to the new one.

408 KGK
Juli/August 2006

 cling technology in this study was also ap-
&
11 &
11 Applications of
plied to tire rubber waste, generated from
reclaimed rubber
for automotive both manufacturing products and scrap
products tires [7].
From the standpoint of the engineering
practice, test truck tires were prepared by
mixing the NR-based reclaimed rubber
(10wt%) from manufacturing products,
with the NR-based new rubber (90wt%)
for the tread rubber compound. Standard
truck tires with only the NR-based new rub-
ber were also prepared for the comparison.
Actual road tests were carried out in mile-
age up to 200 000 km. During the road tests
the changes in the tread depth for both the
test and standard tires were examined
against mileage, respectively. The changes
in the tread depth for the test and standard
truck tires are shown in Figure 12, including
&
12 &
12 Changes in tread equipped positions of those tires on the ve-
depth for stan- hicle. The tread depths were measured
dard and test against mileage for the tires on the rear po-
truck tires during sitions. The tread wear behavior of the test
actual road tests
truck tire was estimated to be almost simi-
lar to that of the standard one in mileage up
to 200 000 km. From these results it was
confirmed that the reclaimed tire rubber
obtained by the continuous recycling tech-
nology can be applied to new tire rubber
compounds with its appropriate content
in the engineering practice.

Recycling process of producing TPE

&
13

Principle of producing TPE

&
13 Dynamic devulcanization and dynamic vulcanization processes for the product of TPE
based on EPDM waste
In 1997 this technology was practically ap-
plied to the material recycling of EPDM
waste generated in manufacturing pro-
cesses of automotive weather strips in a
plant having the production capacity of
500 tons/year for reclaimed rubber [5].
The reclaimed EPDM has been currently uti-
lized for producing various automotive rub-
ber products with its appropriate content as
shown in Figure 11.
Application of continuous recycling
technology to tire rubber waste
The consumed amount of tire rubbers such
as natural rubber (NR), styrene-butadiene
rubber (SBR) and butyl rubber (IIR) for the
production of new tires correspond to about
70 % of the total weight of raw rubber ma-
terials annually consumed in Japan. This re-
sults in one million tons of scrap tires gen-
erated. Hence, the continuous rubber recy-
TPE provides highly recoverable properties
similar to conventional crosslinked rubber,
and can be processed with the moldability
and efficiency of thermoplastics. In addition
to the simpler processing, the principal ad-
vantages of TPE compared to crosslinked
rubber include an easier recycling of waste,
design flexibility, product quality and di-
mensional consistency. Hence, owing to
these excellent characteristics, TPE has
come to be widely used in a variety of ap-
plications including automotive products
as substitute materials for rubbers and
soft plastics. In this study, as the next
step for the development of rubber recy-
cling technology, a more enhanced recy-
cling method of producing a dynamically
vulcanized(crosslinked) TPE based on
EPDM waste has been established [8].
The enhanced recycling process of produ-
cing TPE is composed of pulverization, de-
vulcanization, blend and vulcanization. Fig-
ure 13 shows a schematic illustration of the
recycling of producing the TPE based on
EPDM waste. In the first zone, the crashed
EPDM comes to be pulverized by shearing.

KGK
Juli/August 2006 409

 ROHSTOFFE UND ANWENDUNGEN
RAW MATERIALS AND APPLICATIONS
&
14
&
15
&
16
&
16 Applications of TPE for automotive products
In the following zones, the dynamic devul-
canization (selective breakages of crosslink-
ing points in the EPDM), blend of the re-
claimed EPDM (ca.80wt%) with polypropy-
lene (PP, ca.20wt%), and dynamic vulcaniza-
tion of the EPDM component in the blend
proceed continuously and finally result in
the formation of some desirable domain
structure.
Changes in phase morphology
In order to obtain TPE showing preferable
physical properties, the screw geometry
and configuration for the reactor and reac-
410 KGK
Juli/August 2006
&
14 Temporal changes
in the phase
structure of the
EPDM/PP blends
during the dy-
namic devulcani-
zation and dy-
namic vulcaniza-
tion
&
15 Elongation-retraction property of TPE
Besed on EPDM waste
tion conditions have to be suitably adjusted
to form the desirable domain structure dur-
ing the continuous process. The aiming
morphology of TPE corresponds to the for-
mation of the phase structure with chemi-
cally crosslinked EPDM phase (major com-
ponent) dispersed in PP matrix (minor com-
ponent).
Figure 14 shows the morphology develop-
ment of the EPDM/PP blend during the con-
tinuous process. At the early stage of the
process the EPDM component forms the
continuous phase, depending on its volume
amount in the blend. At the following inter-
mediate and late stages of the process un-
der suitable reaction conditions, the phase
inversion occurs and thus the desirable do-
main structure for TPE, in which the vulca-
nized(re-crosslinked) EPDM phase of less
than 1 lm is finely dispersed in the contin-
uous PP phase, finally comes be formed.
Properties of TPE based on EPDM waste
and its applications for automotive
products
The obtained TPE pellets can be molded by
extrusion molding or injection molding like
conventional thermoplastics. The injection
molded TPE specimen shows good tensile
properties and recovers its original length
after elongation in the elongation-retrac-
tion experiment as shown in Figure 15. In
the engineering practice the TPE based on
EPDM waste is comparable to commercial
TPE in various properties (tensile property,
processability, surface appearance, etc.).
The mass production of the TPE based on
foamed EPDM waste, which is generated
in the manufacturing process of automo-
tive weather strips, has been started in
July 2002 with a new plant having the pro-
duct capacity of 350 tons/year for TPE. The
development of automotive products made
with the TPE as shown in Figure 16 is pre-
sently working on to achieve its practical
uses [9].
Conclusion
In this study, a new recycling technology for
automotive rubber waste has been devel-
oped with twin screw extruder as a modular
screw type reactor. With optimized screw
geometry and configuration in the reactor,
the breakages of crosslinking points may
predominantly occur under suitable condi-
tions of temperature, shear stress and inter-
nal pressure.
Reclaimed rubber from EPDM waste gener-
ated in the manufacturing process of
weather strips exhibits excellent good prop-
erties, which are almost equal to those of
new rubber. The reclaimed rubber has
been currently mass-produced and utilized
for manufacturing automotive rubber pro-
ducts since 1997. It is also confirmed that
this technology can be applied to the recy-
cling of tire rubber waste including scrap
tires. Furthermore, as a next phase of the
development an enhanced rubber recycling
method of producing TPE based on rubber
waste has been established. The TPE shows
physical properties comparable to commer-
cial TPE. The mass production of the TPE
based EPDM waste has been started in
July 2002.
It is expected that the newly developed rub-
ber recycling technology in this study would
contribute to both protecting the environ-
ment and saving resources with regard to
rubber waste generated in the world.
Acknowledgement
This work was partly carried out by joint re-
search and development with International
Center for Environmental Technology
Transfer in 1999-2001, commissioned by
the Ministry of Economy Trade and Indus-
try.
References
[1] ‘‘Recycling of Rubber"", RAPRA Report 99 (1997)
9.
[2] TIRE INDUSTRY OF JAPAN 2005, JATMA, 2005.
[3] Goodyear Tire & Rubber Co. Ltd., Plast. Rubb.
News, Sept. 9 (1979).
[4] A.I. Isayev, J. Chen and A. Tukachinsky, Rubber
Chem. Technol. 68 (1995) 267.
[5] S. Otsuka, M. Owaki, Y. Suzuki, H. Honda, K. Na-
kashima, M. Mouri and N. Sato, SAE Paper 2001-
01-0015 (1998)
[6] K. Fukumori, M. Mouri, N. Sato, H. Okamoto, M.
Matsushita, H. Honda, K. Nakashima, Y. Suzuki
and M. Owaki, Gummi FASERN Kunststoe 54
(2001) 48.
[7] K. Fukumori, M. Matsushita, H. Okamoto, N.
Sato, Y. Suzuki and K. Takeuchi, JSAE Review
23 (2002) 259.
[8] H. Okamoto, K. Fukumori, M. Matsushita, N.
Sato, Y. Tanaka, T. Okita, K. Takeuchi, N. Suzu-
ki and Y. Suzuki, Prepr. of IUPAC-PC2002, Dec.2-
5, 2002, 638.
[9] Y. Tanaka, T. Watanabe, T. Okita, M. Matsushita,
H. Okamoto, K. Fukumori, N. Suzuki and Y. Su-
zuki, SAE Paper 2003-01-0941 (2003).
KGK
Juli/August 2006 411