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Abstract
A new material recycling technology for products shows excellent mechanical properties
crosslinked rubber was developed using the applicable to new rubber compounds.
continuous reactive processing method. In this Furthermore, an enhanced rubber recycling
process of producing reclaimed rubber, breakage process for producing thermoplastic elastomer
of crosslinking points in the crosslinked rubber (TPE) based on rubber waste has been
occurs selectively under the controls of shear established. The TPE obtained exhibits highly
stress, reaction temperature, and internal pressure recoverable rubber elasticity and mechanical
in a modular screw type reactor. Deodorization properties comparable to commercial TPE. It is
during the process has also become possible by a expected that the rubber recycling technology
newly developed method. The reclaimed rubber developed during this study will contribute to
obtained from rubber waste generated from both protecting the environment and also saving
manufacturing products and post-consumer resources.
by optimizing the parameters in the reactor such as complete the devulcanization reaction under shear
shear stress, temperature, and internal pressure. The flow in the next devulcanizing zone. In this reaction
continuous recycling process for crosslinked rubber zone, fine particles of crosslinked rubber become
waste is performed in a modular screw type reactor highly elongated by filling and shearing with the
as schematically shown in Fig. 2. The screw kneading disk elements, and are thus eventually
configuration with the modular screw elements plasticized.
(right-handed screw, kneading disk, etc.) is suitably A basic understanding of the cleavage of
designed to be applicable to a continuous recycling crosslinking bonds under high shear stress is
process. In the first pulverizing zone of this process, suggested as follows. As shown in Fig. 3, there
roughly crushed rubber material is converted into appears to be only a small difference in the bond
fine particles by high shear stress, and heated to the energy between C-C bonds and C-S or S-S bonds.
devulcanization reaction temperature quickly. The Hence, by simple heating in a pressure vessel,
residence time is assured to be long enough to cleavage of both C-C and C-S or S-S bonds may
occur unselectively. This leads to
the lowering of the physical
Crushed rubber waste properties of reclaimed rubber by
the conventional method. On the
other hand, with regard to the
elastic constant k for these bonds
Reclaimed rubber (estimated approximately on the
basis of the values for crystals),
Cooling the k-value for the S-S bonds can
be estimated to be about 1/30th
Pulverizing Devulcanizing that for the C-C bonds, as shown
in Fig. 3(a). Generally, it is
understood that the mechanical
behavior of crosslinked rubber
Fig. 2 Schematic illustration of the reactor for the product of may be mainly controlled by the
reclained rubber.
entropic term in the strain energy.
In contrast with this entropic
deformation behavior, at extremely
higher shear stresses induced by
Elastic constant (relative value) filling and kneading in the reactor,
k CC ( ~100 ) k CS (k CC > k CS > k SS ) k SS ( ~3) most of the rubber molecules may
become fully elongated to their
(a) C C S S limited extensibility. Under these
Bonding energy : conditions, the bonds having lower
E CC : 370 kJ/mol E CS : 310 kJ/mol E SS : 270 kJ/mol elastic constant (the S-S bonds)
may become more extended in
comparison with bonds having
(b) C C S S higher elastic constant (the C-C
bonds), in an elastic manner as
Shear flow
shown in Fig. 3(b). That is, the
elastic energy induced by high
Fig. 3 Breakages of crosslinking points in high shear flow : shearing may be particularly
(a) model for the network chain; (b) deformation of the network
effective on the S-S bonds, causing
chain (particularly, S-S bonds) by shearing.
the selective breakage of
4
10
15
Sol fraction
~0
0
A B C D, E Virgin rubber
Cooling
Position compound
Feeding position
Pulverizing Devulcanizing
E
Sampling positions
A B C D
Mooney viscosity
(ML1+4, 100C)
200
A B
100 D E
C
0
Fig. 5 Appearances and Mooney viscosity of rubbers sampled from the positions A-E.
molecular weight of the sol component during the rubber. Thus, the deodorization procedure appears
process. The average molecular weight of the sol to be quite effective.
component in the reclaimed EPDM is nearly 2. 2. 4 Properties of reclaimed rubber and its
constant, comparable to that of virgin EPDM, from practical uses for automotive rubber
position B to position D. This result supports the products
occurrence of selective breakage of crosslinking The reclaimed EPDM was compounded and
points in the EPDM during the continuous recycling crosslinked with an accelerated sulfur vulcanization
process. system according to the conventional recipe. Figure 9
2. 2. 3 Deodorization of reclaimed rubber shows stress-strain curves for a reclaimed rubber
A characteristic odor arising from reclaimed from the developed method and for a virgin rubber.
rubber sometimes limits its practical application. The reclaimed rubber exhibits an excellent tensile
Hence, a deodorization procedure is also included in stress-strain property, almost comparable to the
the continuous recycling process using a newly virgin rubber.
developed method,7) in which high-pressure water is
injected into the barrel during the devulcanization.
The deodorization mechanism during the continuous : Odorous component
process is schematically shown in Fig. 7 as follows. (a)Untreated
Components in the rubber compound causing the
odor are trapped in the high-pressure water vapor
and removed efficiently through vents with vacuum Signal intensity
pumps. The barrel temperature and screw elements (b)Treated
around the positions for water injection are suitably
adjusted to avoid inadequate progress of the
devulcanization caused by the decreased temperature (c)NR-based
through the diffusion of water molecules. Figure 8 rubber
compound
shows gas chromatography signals of the odorous
components in reclaimed rubbers (both untreated
Odorous components
and treated) and virgin rubber compound. For the
reclaimed rubbers, the odorous components in the
treated rubber are barely detected, similar to the
Fig. 8 Signals from odorous components in
virgin rubber compound, while there are many rubbers.
odorous components detected in the untreated
Reclaimed Break
rubber
10
Stress ( MPa)
Virgin rubber
0
0 300 600
Strain (%)
In 1997, this technology was put to practical and the standard tire were examined against the
application in the material recycling of EPDM waste mileage driven. The changes in the tread depth for
generated in manufacturing processes of automotive the test and standard truck tires are shown in Fig. 11,
weather strips in a plant having production capacity along with the positions of the tires on the vehicle.
of 500 tons/year for reclaimed rubber 5) . The The tread depths were measured against mileage for
reclaimed EPDM is currently being utilized for the tires on the rear positions. Based on the results,
producing various automotive rubber products, as the tread wear behavior of the test truck tire is
shown in Fig. 10. estimated to be similar to that of the standard tire for
2. 2. 5 Application of continuous recycling mileages up to 200,000 km. These results confirmed
technology to tire rubber waste that the reclaimed tire rubber obtained by the
The amount of various rubbers, such as natural continuous recycling technology can be applied to
rubber (NR), styrene-butadiene rubber (SBR) and new tire rubber compounds with appropriate content,
butyl rubber (IIR), consumed for the production of suitable for practical engineering. This recycling
new tires correspond to about 70% of the total technology of tire rubber waste was licensed out to
weight of raw rubber materials annually consumed Yokohama Rubber Co., Ltd. in 2001.
in Japan. This results in one million tons of scrap 2. 3 Recycling process of producting TPE
tires generated per year. Hence, the continuous 2. 3. 1 Principle of producing TPE
rubber recycling technology in this study was also Thermoplastic elastomer (TPE) possesses highly
applied to tire rubber waste, generated from both recoverable properties similar to conventional
manufacturing products and scrap tires, 7) to crosslinked rubber, and can be processed with the
investigate its application potential here. moldability and efficiency of thermoplastics. In
Test truck tires were prepared by mixing NR-based addition to simpler processing, the principal
reclaimed rubber (10 wt%) from manufacturing advantages of using TPE compared to crosslinked
products treated by the continuous recycling process rubber include easier recycling of waste, design
with NR-based virgin rubber (90 wt%) for the tread flexibility, product quality and dimensional
rubber compound. Standard truck tires using only consistency. Hence, owing to these excellent
NR-based virgin rubber were also prepared for characteristics, TPE is now widely used in a variety
comparison. Actual road tests were carried out at of applications, including automotive products, as
mileages up to 200,000 km. During the road tests, substitute material for rubbers and soft plastics. In
the changes in the tread depth for both the test tire this study, as the next step in the development of
Fig. 10 Applications of reclaimed rubber for Fig. 11 Changes in tread depth for standard and test
automotive products. truck tires during actual road tests.
rubber recycling technology, a more enhanced component in the blend proceed continuously and
recycling process of producing a dynamically result finally in the formation of a product with
crosslinked TPE based on EPDM waste has been desirable domain structure.
established.8) 2. 3. 2 Change in the phase structure during
The enhanced recycling process of producing TPE the recycling process
is composed of pulverizing, devulcanizing, blending, In order to obtain TPE showing preferable
and dynamically crosslinking procedures. Figure 12 physical properties, the screw geometry and
shows a schematic illustration of the recycling of configuration of the reactor and the reaction
EPDM waste to produce the TPE. In the first zone, conditions during the continuous recycling process
crushed EPDM is pulverized by shearing. In the have to be suitably adjusted to form the desirable
following zones, the devulcanization (selective domain structure in the product. The target
breakage of crosslinking points in the EPDM), morphology of the TPE corresponds to formation of
blending of the reclaimed EPDM with a phase structure with the chemically crosslinked
polypropylene (PP, ca. 20 wt% to ca. 80 wt% EPDM phase (major component) dispersed in a PP
EPDM), and the dynamic crosslinking of the EPDM matrix (minor component). Figure 13 shows the
Deodorizing
Degassing
EPDM Water
waste
PP
Additives
Cooling TPE
Fig. 12 Continuous recycling process for the product of TPE based on EPDM waste.
Fig. 13 Temporal changes in the phase structure of the EPDM/PP blend during the continuous
recycling process.
temporal changes in the phase structure of the 2. 3. 3 Properties of TPE based on EPDM
EPDM/PP blend during the continuous recycling waste and its applications for
process. At the early stage of the process, the automotive products
EPDM component forms the continuous phase, The obtained TPE pellets can be molded by
depending on its volume amount in the blend. At extrusion molding or injection molding methods,
the following intermediate and late stages of the like conventional thermoplastics. Injection molded
process and under suitable reaction conditions, TPE specimens showed good tensile properties and
inversion of the phase structure occurs. The desired recovered its original length after elongation in an
TPE domain structure, in which a re-crosslinked elongation-retraction experiment, as shown in Fig. 14.
EPDM phase of less than 1 m is finely dispersed in In engineering practice, this TPE based on waste
the continuous PP phase, is then formed. EPDM is comparable to commercial TPE in various
properties, including tensile property, processability,
and surface appearance.
Mass production of TPE based on foamed EPDM
6 waste, which is generated in the manufacturing
process of automotive weather strips, was started in
Stress ( MPa)
Mitsumasa Matsushita
Year of birth : 1958
Division : Organic Materials. Lab.
Research fields : Reactive processing of
polymer blends and composites,
Polymer recycling
Academic society : The Soc. of Polym.
Sci., Jpn.