ROHSTOFFE UND ANWENDUNGEN
RAW MATERIALS AND APPLICATIONS
Recycling
Rubber powder
Chemical
modification
Grafting
In material-sensitive recycling of
crushed reclaimed rubber materials,
which is achieved by admixing the re-
cycled rubber with new rubber ma-
trices, a drop is noted in the mechani-
cal value level of elastomers. This
drop is due to deficient grafting of the
recycled rubber with the fresh rubber
matrix. To improve grafting quality, the
particle surfaces are modified chemi-
cally in different ways following a
comprehensive morphological and
chemical characterization of select
types of rubber powder. Grafting with
maleic anhydride and grafting of re-
active silane-based coupling agents
following epoxidation or hydroxylation
have shown themselves to be the
most promising methods. The criter-
ion applied to evaluate the suitability
and effects of the surface modifica-
tion is the level of or the observable
changes in the material's mechanical
properties, such as, for example, frac-
ture stress and dynamic modulus.
PhasengrenzflaÈchenhaftung
von zerkleinertem Altgummi
Recycling
Gummimehl
Chemische
Modifizierung
Anbindung
Die stoffliche Wiederverwertung von
zerkleinertem Altgummi durch Zumi-
schen zu neuen Kautschukmatrices
ist auf Grund mangelnder Anbindung
¹Altgummi ± frische Kautschukmatrixª
mit einem Abfall des mechanischen
Werteniveaus des Elastomeren ver-
bunden. Zur Verbesserung der Anbin-
dung werden verschiedene chemische
Modifizierungen der PartikeloberflaÈ-
chen nach einer umfassenden mor-
phologischen und chemischen Cha-
rakterisierung von ausgewaÈhlten
Gummimehlen vorgenommen. Als
aussichtsreiche Methoden haben sich
sowohl die Pfropfung mit MaleinsaÈu-
reanhydrid als auch die Epoxidierung
bzw. Hydroxylierung mit anschlieûen-
der Anbindung von Kopplungsagen-
zien auf Basis reaktiver Silane her-
ausgestellt. Als Kriterium zur Beurtei-
lung der Tauglichkeit und Effekte der
OberflaÈchenmodifizierung dient das
Niveau bzw. die beobachteten AÈnde-
rungen in den mechanischen Werk-
stoffeigenschaften, wie z. B. die
Bruchspannung und der dynamische
Modul.
218
Interphase Grafting of Reclaimed
Rubber Powder
A. Amash, U. Giese, R. H. Schuster, Hannover
As the production and use of rubber ar-
ticles steadily increases, there is neces-
sarily a concomitant rise in the incidence
of discarded rubber. In the United States
alone 170,000 metric tons of production-
related rubber scrap is generated each
year. This constitutes 5 % of overall pro-
duction. In Germany approx. 550,000
metric tons of discarded tires accumulate
each year, and the amount is likely to con-
tinue to rise. Only a small portion of the
discarded tires is retreaded [1 ± 3].
It is a well-known fact that direct mate-
rial recycling and reshaping is difficult be-
cause of the irreversible three-dimen-
sional crosslinking of rubber. Countless
attempts have nonetheless been pro-
posed for material-sensitive recycling of
rubber [1 ± 10].
Thanks to a favorable energy balance,
the lion's share (approx. 60 %) of the dis-
carded tires disposed of is recycled as
energy in cement factories and power
stations. This method does not, of
course, represent the kind of material-
sensitive recycling alternative one would
want to strive for. It is ecologically ques-
tionable and has undesirable implications
for the future in terms of the conservation
of resources and a targeted reduction in
the negative impact on the environment.
There are a number of methods that can,
in principle, be applied to meet these tar-
gets: pyrolysis, hydrogenation (combin-
ing or treating with hydrogen) and high-
temperature atomization [3, 9]. Due to
their low economic efficiency these meth-
ods enjoy only minor consideration as re-
cycling concepts at the moment.
One of the most proven raw-material-
sensitive recycling methods for discarded
rubber is what is referred to as regenera-
tion or devulcanization. A number of dif-
ferent methods are possible here: chemi-
cal, mechanical, thermomechanical,
cryogenic-mechanical, microwave and
KGK Kautschuk Gummi Kunststoffe 55. Jahrgang, Nr. 5/2002
ultrasonic [10 ± 16]. To be sure, these var-
iants are disadvantageous in terms of
product quality and efficiency. Most sig-
nificantly, one of the results actually tar-
geted ± a decrease in sulfur bridges ±
has an undesirable side effect, that of a
drop in the performance level of the re-
claimed rubber due to significant depoly-
merization on the polymer chains.
Today a small portion of the discarded
rubber (< 10 %) is reduced to crumb or
powder and used as a minor aggregate
component in the production of new rub-
ber compounds. A problem in this is that
the rubber particles represent foreign
bodies in vulcanized material. This is
due to their having already been vulca-
nized and forming only a relatively minor
particle surface component. As a result
they interact only weakly with the ambient
fresh rubber matrix and thus exhibit poor
grafting quality, producing weaknesses in
the material at certain points and detract-
ing from the mechanical properties [2, 3,
17 ± 20]. This negative effect is slightly re-
duced by using rubber powder with a
small particle size and structured surface
quality, in which case the grafting quality
is essentially influenced by physical
forces.
In general, grafting of two different
polymer phases is achieved in a blend
with adequate thermodynamic compat-
ibility by interdiffusion of the molecular
chain in the area of the phase boundary
[21, 22]. This process rarely occurs in the
case of rubber compounds containing re-
cycled rubber. The reason for this is the
prevailing crosslinking of the polymer ma-
trix of the recycled rubber particles, even
in the case of polymer systems that are, in
principle, thermodynamically compatible.
The basic precondition for high molecular
chain mobility is not adequately provided.
A very promising solution to this problem
is that of grafting recycled rubber particle

as a result of interdiffusion and a principal
chemical valence bond by chemically
modifying the surface of the rubber pow-
der particles. Any existing double bonds
in the recycled rubber powder matrix can
be used as reactive centers for functiona-
lization. When covulcanizing the recycled
rubber and the fresh rubber matrix it
should then be possible by means of
coupling agents to completely graft the
recycled rubber particles chemically
onto the rubber matrix and achieve an im-
provement in the mechanical ± and in
particular, the mechanical-dynamic ± per-
formance level of the resulting elasto-
mers.
Experimental aspects
The following steps describe the full ap-
proach taken in developing methods for
chemically grafting recycled rubber onto
a rubber matrix that is to be freshly vulca-
nized:
± physical and chemical characterization
of recycled rubber powder
± chemical modification of the particle
surfaces of reclaimed rubber powder
± manufacture of compounds containing
rubber powder with particle grafting
± comparative characterization of vulca-
nizate and reference specimens
A total of five rubber powder types avail-
able commercially are considered. Along-
side two coarse-grained warm or warm
and cryogenic reground rubber powder
types (types A and B) with a particle
size < 600 lm (according to the manu-
facturer), three fine-grained warm and
then cryogenically reground rubber pow-
der types (type C, D and E) from truck tire
a)
Fig. 1. Particle size distribution of coarse- and fine-grained rubber powder (types A and D)
220
Interphase Grafting . . .
treads with a particle size < 160 lm (ac-
cording to the manufacturer) were also
considered.
Chemical and physical charac-
terization methods
Characterization of the morphology
The particle size distribution and the sur-
face structure of the rubber powder were
determined using an optical microscope
[23]. In a transparent EPDM matrix (film,
thickness < 120 lm) dispersed rubber
powder was viewed microscopically un-
der 32-fold enlargement. To obtain statis-
tically significant values, approximately
2000 ± 2500 particles from the em-
bedded rubber particles were analyzed.
The mean grain size G was calculated as
mean weight GW and mean number Gn,
with the distribution range V resulting
from (GW/Gn )-1 [23].
The roughness of the surface-descrip-
tive fractal dimension c for the circumfer-
ence can be determined on the basis of
the magnitude of the particle projection U
and the particle surface. The anisometric
factor F I is described by the maximum
extension of the projection surface and
of the diameter of a circular surface
equivalent to the particle.
Chemical characterization
The concentration of double bonds, a
factor that is extremely interesting in esti-
mating chemical reactivity, was deter-
mined on the particle surface by means
of titration with an aqueous potassium
permanganate solution in alcohol.
b)
KGK Kautschuk Gummi Kunststoffe 55. Jahrgang, Nr. 5/2002
Soxhlet extraction is applied to sepa-
rate soluble low-molar ingredients from
the elastomer matrix of the rubber pow-
der. Plasticizers and other additives were
determined by means of liquid chromato-
graphy (LC) and FT-IR spectroscopy [24,
25].
The polymers were identified by means
of pyrolytic FT-IR spectroscopy [26, 27]
and dynamic difference calorimetry
(DDC) [28 ± 30]. An overview of the quan-
titative composition of the rubber powder
types was obtained with the help of ther-
mogravimetric analysis (TGA) [27 ± 29].
Results of the characterization
of rubber powder types
Morphology
Fig. 1 provides a representative display of
the results for particle size distribution of a
ªfine-grainedº rubber powder ± type D ±
and of a ªcoarse-grainedº rubber powder
± type A. As would be expected, rubber
powder of type D exhibits a markedly low-
er particle size and a narrower distribution
of particle size than the contrasting
coarse-grained type A (Fig. 1).
Tab. 1 summarizes the data from the
measurements of surface structure and
specific surface. The relatively intensive
follow-up cryogenic comminution of the
rubber powder types C, D and E provides
a particle surface of lesser roughness and
of a lower anisometric factor than does
warm grinding, e.g. in the case of rubber
powder type A (Tab. 1). The specific sur-
face was calculated with the median of
the particle size distribution (Gn), assum-
ing spherical symmetry and a density of
 Interphase Grafting . . .

Tab. 1. Morphological characterization and double bond concentration

Rubber powder (RP) Type A Type B Type C Type D Type E
Median number Gn [lm] 284 195 51 54 57
Median weight GW [lm] 487 331 77 83 88
Distribution range V 0.71 0.69 0.50 0.53 0.54
Anisometric factor F 1.56 1.52 1.49 1.5 1.5
Fractal dimension of circumference c 1.11 1.08 1.06 1.06 1.06
Specific surface [m2/g] 0.019 0.027 0.076 0.099 0.093

Tab. 2. Results of the chemical analysis of fine-grain rubber powder of type D and of coarse-grain rubber powder of type A
Ingredient Constituent Weight-% Method
Fine powder Coarse-grained
powder
Polymer NR 38.4 38.1 TGA , DSC, pyrolysis, FT-IR
SBR 16.2 16.8
Fillers carbon black 30.4 29.6 TGA
Minerals (calcined residue) metal oxide 7.1 7.8 TGA
Extractable parts low-molar ingredients 7.9 8.0 Extraction (methylene chloride)
Plasticizers (hydrocarbons) paraffinic/naphthenic HC 3.1 3.2 Extraction LC, FT-IR
aromatic HC < 5.5 < 5.8 Extraction LC, FT-IR
Antioxidant PPD < 2.5 ± < 2.7 Extraction LC, FT-IR
Remark: TMQ
Abbreviations used in Tab. 2.
HC ± hydrocarbons
PPD ± p-phenylenediamine
TMQ ± 2,2,4-trimethyl-1,2-dihydrochinoleine

von 1.1 g/cm3. Because of its low particle
size, relative narrow particle size distribu-
tion range (homogeneity) and more favor-
able value as regards particle structure,
the fine-grained rubber powder type D
seemed particularly well suited for further
study of the morphological aspects of
grafting to a fresh rubber matrix.
Chemical composition
Depending on aging and comminution
process, the originally unsaturated princi-
pal polymer chain exhibits an adequate
double bonding concentration.
Applying the aforementioned method,
rubber powder type D was shown to
have the highest double bond concentra-
tion 3.8*10 4 mol/g; types C and E had
1.8*10 4 mol/g and 3.5*10 4 mol/g re-
spectively. The comparative values for
coarse-grained rubber powder are
1.4*10 4 mol/g and 1,7*10 4 mol/g.
The chemical composition of rubber
powder type A and type D are summar-
ized in Tab. 2.
The chemical composition of the two
rubber powder types A and D is extre-
mely similar. The results hint at the
same origin for both types of powder.
The polymer base in each case is a blend
of NR and SBR, accounting for a total
share of roughly 58 % of the compound,
blended at a ratio of 2.4:1. Carbon black
is the sole filler added to these rubber
powders (approx. 30 %). Low-molar in-
gredients make up the extracted shares
(approx. 8 %) and consist mainly of plas-
ticizers, antioxidants and processing
agents. The total share of these sub-
stances is much lower than in new mate-
rials (tire formulas). This points to a reduc-
tion in volatile constituents as a result of
aging during use and perhaps also
from the crushing and grinding process.
Previous extraction can prevent the
low-molar ingredients ± especially the
antioxidants ± from subsequently exert-
ing any negative influence on chemical
modification of the rubber powders.
Conclusions drawn from the
characterization of the rubber
powders
The morphological characterization of the
rubber powders shows that type D fine
rubber powder exhibits the more favor-
able prerequisites for chemical grafting.
Chemical analyses indicate that despite
oxidative influences during use and in
the crushing and grinding process, pow-
der from discarded rubber still possesses
a primary prerequisite for chemical mod-
ification, namely reactive double bonds in
the polymer chain. It is advisable to ex-
tract low-molar constituents such as anti-
oxidants from the discarded rubber to
prevent any negative impact on chemical
modification.
On the basis of the results obtained as
regards morphology, double bond con-
tent and chemical data, only the fine-
grained type D rubber powder is used
for purposes of chemical modification
and to make new compounds.
Modification of the particle
surface of rubber powder
Grafting with maleic anhydride
Using maleic anhydride (MSA) to produce
grafted polymers is, in principle, a well-
known method for chemical modification
[31 ± 33].

KGK Kautschuk Gummi Kunststoffe 55. Jahrgang, Nr. 5/2002 221

 Interphase Grafting . . .

Experimentally the epoxidation of re-

Fig. 2 shows two different reaction possi-
bilities that can be expected in grafting
MA onto NR depending on the condi-
tions ± e.g. temperature and radical
initiator ± under which the reaction oc-
curs.
This reaction involves both intermole-
cular addition of the ethylene derivative
to the polymer's double bonds, with the
participation of one or more chains per
MSA molecule (Fig. 2a), and the adsorp-
tion onto carbon atoms in the a position
of the methylene groups, likewise under
the reaction of the respective MSA mole-
cule with one or two adjacent polymer
chains (Fig. 2b). If carried out in the pre-
sence of peroxide, the grafting reaction
can, in principle, be conducted in an
emulsion or in a solid substance [34],
with the final variant being applied here.
In the case of this variant, MA is al-
lowed to react with the polymatrix of
the rubber powder at a high temperature
(approx. 200 8C) directly in the kneader
for ten minutes. At moderate speed the
rubber powder and MSA are mixed in
the mixer in a weight ratio of 80:20,
with little dicumylperoxide (DCP) being
added. The manufacture of the subse-
quent compound occurs immediately
after this process.
With the help of FT-IR spectroscopy it
was possible to provide proof of the suc-
cessful grafting of MA at the particle sur-
face on extracted material (vibration band
of MA at 1780 cm 1).
Fig. 2. Grafting of
maleic anhydride
(MA) onto natural
rubber
and unsaturated polymers to form the
corresponding epoxy compounds.
The literature contains countless pub-
lished studies on the modification of NR
to epoxidated NR (E-NR) [35 ± 37]. The
degree of epoxidation is essentially a
function of the temperature and duration
of the reaction and the strength of the or-
ganic acid. Excessively high temperature
and long reaction times ± above all in
acidic media ± lead to an undesirable
ring opening of the epoxies with second-
ary reactions in connection with the for-
mation of glycols or their ethers (Fig. 3).
Fig. 3. Side reac-
tions of epoxidation,
taking the example
of NR, a) hydrolysis
of epoxy to alcohol,
b) formation of ether
bridges, c) forma-
tion of tetrahydro-
furan groups
claimed rubber powder was carried out
in the following way:
Extracted rubber powder is stirred in
dichloromethane for approx. 10 hours.
Chloroperbenzoic acid dissolved in di-
chloromethane is added to induce the
epoxidation of the rubber powder sus-
pension. After a reaction time of 24 hours
at room temperature, the solution is pre-
cipitated and the precipitate filtered,
washed and dried.
The grafting of water onto 1,2-epoxyde
is exploited for a concluding hydroxyla-
tion with formation of 1,2 dihydric alcohol.
To obtain a complete reaction in the ab-
sence of catalysts, hours-long heating is
necessary at a temperature in excess of
100 8C. If the oxirane ring is adjacent to a
tertiary C atom, as, for example, in the
case of isoprene or polyisoprene, water
triggers hydrolytic splitting already at
room temperature.
Epoxidated rubber powder is thus trea-
ted at room temperature with an excess of
distilled water for a week under constant
stirring. It is then filtered and dried.
Successful hydroxylation of the rubber
powder could be proven by means of FT-
IR spectroscopy. Fig. 4 shows the IR
spectrum for the hydroxylated rubber
powder.

Epoxidation and hydroxylation

Fig. 4. FT-IR spec-
Organic per-acid, such as, for example, trum of hydroxy-
per-benzoic acid, react with alkylenes lated rubber powder

222 KGK Kautschuk Gummi Kunststoffe 55. Jahrgang, Nr. 5/2002

 Interphase Grafting . . .

Tab. 3. Formulas for the rubber-powder compounds and reference compounds used (all data in phr)
Constituent Ref. 1 Ref. 2 C1 C2 C3 C4 C5 C6 C7 C8
SBR-1500 100 70 ± ± 70 ± 100 70 70 70
SBR-g-MSA ± ± 70 70 ± 70 ± ± ± ±
RP ± 30 ± 30 ± ± ± 30 ± ±
RP-g-MA ± ± ± ± 30 30 ± ± ± ±
hydr. RP ± ± ± ± ± ± ± ± 30 30
IR-g-MA ± ± ± ± ± ± ± ± ± 10
Ethylene glycol ± ± ± ± 4 4 ± ± ± ±
MgO ± ± ± ± 4 4 ± ± ± ±
MA ± ± ± ± 5 5 - ± ± ±
TESPT ± ± ± ± ± ± 4 4 4 ±
ZnO 4 4 4 4 4 4 4 4 4 4
Stearic acid 2 2 2 2 2 2 2 2 2 2
Sulfur 1.75 1.75 1.75 1.75 1.75 1.75 1.75 1.75 1.75 1.75
CBS 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25
Abbreviations:
Ref. reference compound g ªgraftº (chemically modified)
C compound MA maleic anhydride
RP rubber powder TESPT Bis-(3-triethoxysilylpropyl)-tetrasulfide
hydr. hydroxylated

Compared to extracted original pow-
der, the hydroxylated rubber powder dis-
plays a much more pronounced and
wider OH band in the 3000 ± 3700
cm 1 range and particularly intensive
and broad absorption of the C-O bonds
in the 1000 ± 1200 cm 1 range. The con-
spicuously stepped-up intensity of the
deformation bands in the 1300 ± 1400
cm 1 range, moreover, point to broad
(C-OH) underground absorption of an in-
creased magnitude. Alcohols are reliably
identifiable in all the absorption ranges re-
ferred to.
The hydroxyl groups formed can now
be of good use in coupling reactions on
fresh rubber using suitable agents.
Manufacture of compounds and
vulcanizates
Compounds
compatibility agents) were made in a
lab test mixer (Haake E-380). The speci-
fied mixing temperature in the kneader is
75 8C, the rotor speed 50 rpm and the
mixing time ten minutes. In a second
stage the crosslinking agents (sulfur
and accelerator) are admixed on a lab
mill at 50 8C with a homogenization
time of five minutes.
In the case of compounds 3 and 4 the
compound in the mixer ± i.e. the com-
pound resulting from the process of mod-
ifying the rubber powder with MSA (see
ªGrafting with MAº) ± is additionally mixed
with 4 phr ethylene glycol 4 phr MgO and
5 phr pure MSA as phase mediator and
the standard crosslinking system for six
minutes in accordance with Tab. 3. While
the anhydride molecules of the grafted
coupling reagent MA and the rubber
powder can be chemically linked to one
another by esterification via the bifunc-
tional alcohol ethylene glycol, the polymer
chains of the rubber matrix can subse-
quently be covulcanized with sulfur and
accelerator. Pure MA serves as phase
mediator, among other things.
In the case of compound 7, hydroxy-
lated rubber powder is bound to the
SBR matrix with the help of coupling
agents. A commercial bifunctional orga-
nosilane ± Bis-(3-triethoxysilylpropyl)-tet-
rasulfide (TESPT), to cite just one agent ±
is available for this purpose [38, 39]. This
silane is normally used in the preparation
of rubber compounds with silicatic (OH
group bearing) fillers. Fig. 5 shows the re-
action of the reactive TESPT ethoxy
groups with filler silanole groups.
Ethanol is released in the modification
reaction, resulting in the formation of an
intermediate reactive product. The tetra-
sulfide group of the filler/TESPT reaction
product reacts in a coupling reaction,

E-SBR (Intol 1500) is used as fresh rubber

matrix. In accordance with the aforemen-
tioned relationships, suitable cross-link-
ing systems ± e.g. on the basis of anhy-
drides and corresponding acids ± are
used for gating modified rubber powders.
The composition of the compounds pre-
pared, including comparative com-
pounds, is based on the following formu-
las:
The compounds of rubber and rubber
Fig. 5. Silanization
powder as well as ZnO stearic acid and, reaction of silicic
in certain cases, other additives (e.g. acid with TESPT

KGK Kautschuk Gummi Kunststoffe 55. Jahrgang, Nr. 5/2002 223

 Interphase Grafting . . .

preferably in combination with vulcaniza-
tion accelerators (with and without sulfur),
forming crosslinking points with double-
bond-bearing types of rubber (NR, SBR
etc.).
A further possibility for coupling the hy-
droxylated rubber powder onto the rub-
ber mix is to use MSA-g-IR (maleic anhy-
dride grafted polyisoprene, in a fluid
state), as shown in the case of compound
8. While esterification by means of ring
opening occurs on the one hand, the
coupling agent's polymer chain can, on
the other hand, be crosslinked with the
rubber via sulfur bridges.
2-mm slabs were vulcanized in a press
at T ˆ 160 8C and a press pressure of
180 bar. The crosslinking time results
from the t90-value, which is determined
on the basis of vulcametric measure-
ments (Monsanto rheometer) plus two
minutes.
Properties of compounds
containing rubber
Characterization methods
the readings obtained in tensile testing.
In general it is evident that the material's
elongation at break decreases with the
admixture of MA to the rubber during
the mixing process. To be sure, this is ac-
companied by a marked improvement in
rupture stress. The highest stress value is
delivered by the specimen containing
both modified rubber as fresh matrix
and grafted rubber powder. Good cross-
linking of the whole matrix can serve as
an explanation for this. The conclusion
to be drawn is that modification in a solid
substance provides a suitable method for
grafting reclaimed rubber powder.
Influence of post-hydroxylation
grafting
As mentioned above, TESPT, a bifunc-
tional polysulfidic organosilane, was
used to graft the hydroxylated rubber pow-
der to the new rubber matrix. The success-
ful chemical reaction between the pow-
der's OH groups and the silane's ethoxy
groups could be demonstrated by the
ethanol released (headspace-GC-MS).
The mechanical properties of vulcani-
zates based on SBR and hydroxylated
rubber powder was first characterized
by means of tensile testing (Fig. 7).
While it is generally evident that silane
brings about a drastic reduction in elon-
gation at break, it increases tensile
strength just slightly. This can be ex-
plained mainly by an increase in cross-
linking points in the rubber matrix. Unfa-
vorable mixing conditions play a major
role in the case of compounds containing
rubber. These conditions include, for ex-
ample, a temperature that is not optimum
for the reaction between polymer and si-
lane.
On the basis of the mechanical data it
is also possible to conclude that the in-
corporation of strictly hydroxylated rub-
ber powder free of silane additives gives
rise to a particularly marked increase in
elongation at rupture and a reduction in
rupture stress. This effect can be attribu-
ted to the increase in the powder parti-
cles' chemical polarity as a result of hy-
droxylation, leading to a certain incom-
patibility with the rubber matrix.

Strain-stress measurements were con-

ducted at room temperature on a univer-
sal testing machine (Zwick) with optical
length-change sensor in accordance
with DIN. The uniaxial deformation was
effected at a deformation speed of
20 mm/min. The performance level and
the chemical pretreatment were evalu-
ated in all cases on the basis of the tensile
strength (rmax) and elongation values (eb) Fig. 6. Results of
at break. tensile testing
carried out on
Dynamic-mechanical analyses (DMA) MA grafted
were characterized on select compounds rubber powder
by means of temperature-dependent (S = SBR, G = rubber
powder, m = maleic
measurements taken at a frequency of
anhydride)
1 Hz in torsion with ªrheometric dynamic
analyzerº (RDA II).

Results for vulcanizates with

modified rubber powders

Influence of grafting with maleic

grafting
In order to determine the influence of cer- Fig. 7. Results of
tensile testing
tain components, the vulcanizates were carried out on
subjected to comparative mechanical hydroxylated
characterization on the basis of the for- rubber powder
mulas in Tab. 3, with the strength level (S = SBR, i = TESPT,
G = rubber powder,
serving as the criterion for evaluation of h = hydrose, m =
the interphase grafting. Fig. 6 shows maleic anhydride)

KGK Kautschuk Gummi Kunststoffe 55. Jahrgang, Nr. 5/2002 225


Adding MA-graft-IR instead of silane
greatly increases the vulcanizate's elon-
gation at rupture and reduces its rupture
stress even further. This can be attributed
to the inherent properties of the highly vis-
cous polymer fluid added, which pro-
duces here simultaneously both an inter-
phase grafting and a plasticizers effect. It
is conceivable that a reduction in both the
degree of hydroxylation and in the
amount of the coupling agent added is
necessary to achieve better results.
The silane vulcanizates manufactured
are subjected to dynamic-mechanical
analysis. Fig. 8 shows the corresponding
results. The specimen with hydroxylated
rubber powder exhibits a slightly higher
module than the compound with the un-
treated powder. What's more, a slight up-
ward shift in the rubber matrix's glass
transition temperature is also evident.
This points to an improvement in the
compatibility of the components and
thus in the mechanical-dynamic proper-
ties.
Summary
The tested methods for chemical modifi-
cation of rubber powder ± i.e. the grafting
of maleic anhydride and epoxidation or
hydroxylation followed by coupling reac-
tions ± are to be deemed the most pro-
mising and suitable processes. Despite
the fact that the modification variants stu-
died still do not provide a clearly satisfying
performance level for compounds con-
taining recycled rubber powder, they do
apparently allow for grafting the treated
powder particles onto the new rubber
phase. This can be confirmed by the
complete results of the physical and che-
mical characterization. The testing and
226
Interphase Grafting . . .
Fig. 8. Mechanical-
dynamic results for
compounds with
hydroxylated rubber
powder
reaction conditions selected in the pre-
treatment (temperature, duration of reac-
tion, admixture of coupling reagents etc.)
have a crucial influence on the physical
and chemical property profile of the elas-
tomers containing rubber powder.
As part of the continuing work on sur-
face modification of discarded rubber
aimed at achieving an optimum grafting
on a fresh rubber matrix, it is particularly
important to optimize the reaction para-
meters and conditions of MA grafting
and of epoxidation and hydroxylation.
Acknowledgements
The authors greatly acknowledge the fi-
nancial support provided by the Umwelt-
bundesamt (Berlin) and by Vredestein
Rubber Resources (Maastricht, NL).
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The authors
Dr. U. Giese is head of the elastomer chemistry de-
partment, Dr. A. Amash is manager of the processing
department and Prof. Dr. R. H. Schuster is director of
the ªDeutsches Institut fuÈr Kautschuktechnologie e.V.
(DIK)º in Hannover
Corresponding author
Deutsches Institut fuÈr Kautschuktechnologie e.V.,
Dr. U. Giese
Eupener Str. 33, D-30519 Hannover