EPDM RUBBER PLASTICIZED WITH POLYMERIC SOYBEAN OIL OF

DIFFERENT MOLECULAR WEIGHTS

ZORAN S. PETROVIĆ,1,* JELENA MILIĆ,1 MIHAIL IONESCU,1 JAMES R. HALLADAY2

1
PITTSBURG STATE UNIVERSITY, KANSAS POLYMER RESEARCH CENTER, PITTSBURG, KS 66762
2
LORD CORPORATION, ERIE, PA 16505

RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 90, No. 4, pp. 667–682 (2017)

ABSTRACT
Polymerization of soybean oil produces higher-viscosity liquids, which may serve as processing aids and plasticizers in
certain rubbers as a replacement of petrochemical oils. Four polymerized soybean oils of different molecular weights showed
good compatibility with ethylene–propylene–diene rubber (EPDM), but because of the presence of double bonds and
copolymerization with EPDM, they decreased the cross-linking density when compared with paraffinic extender oil. As a
consequence, polymeric soybean oils reduced tensile strength and modulus but increased elongation, tear strength, and
compression set. Higher-molecular-weight plasticizers are expected to reduce sweating out of oils. Pure soybean oil was not
completely compatible at the concentration tested, but it showed a strong plasticizing effect; dramatically lowered tensile
strength, tear strength, and modulus; and increased elongation and compression set. No clear effect of molecular weight of
polymerized soybean oils on properties was observed, but increasing the sulfur content was found to be beneficial. Using
polymeric vegetable oils instead of petrochemical extenders in EPDM rubbers is economical and environmentally desirable,
but the curing system requires optimization to accommodate loss of cross-linking density. [doi:10.5254/rct.18.82690]

INTRODUCTION
Ethylene propylene rubber is a general purpose elastomer with a fully saturated backbone
having excellent resistance to oxygen, heat, ozone, weathering, and steam. Generally, during
manufacture of the polymer, a diene monomer is added, and the resulting terpolymer is known as
EPDM. EPDM rubbers contain between 40 to 80 weight % ethylene and between 4% and 8% diene.
EPDM can be cross-linked with either peroxide or sulfur and finds use in seals, hoses, weather
stripping, and electrical cable.
The most widely used plasticizers for EPDM are naphthenic petroleum oils, but paraffinic oils
are recommended for higher-temperature applications or for peroxide cures. EPDM compounds
often use very high levels of plasticizer, and some commercial polymers are supplied in oil-
extended grades with up to 100 parts per hundred rubber (phr) oil. Without plasticizer, EPDM is dry
and very difficult to mix and process. Plasticizers solubilize the EPDM rubber and assist in
Brownian motion of the polymer chains, thus reducing the viscosity of the compound and
improving the flow characteristics. Because of environmental and sustainability concerns, it is
desirable to replace some petrochemical component with renewable materials. Following this
trend, attempts have been made to replace mineral oil with vegetable oils as processing aids and
plasticizers in rubbers. In our previous publication,1 we discussed the use of soybean oil (SBO) and
polymerized SBO as plasticizers for natural rubber (NR) and styrene–butadiene rubber (SBR) and
found excellent compatibility. Pure SBO had the strongest plasticizing effect, but polymerized oils
could be incorporated at higher concentrations. We did not find evidence of copolymerization of
rubber and oil to a substantial degree, probably because of the abundance of double bonds in NR and
SBR. In the meantime, several publications appeared on the use of different oils (olive and orange,2
palm,3 linseed,4 or rice bran oil5 ) in different rubbers.2–4 Biodiesel was found to have excellent
compatibility with NR, SBR, and polybutadiene.6 When palm oil was compared with paraffinic oil

*Corresponding author. Ph: 620-235-4928; email: zpetrovic@pittstate.edu

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TABLE 1
CHARACTERISTIC PROPERTIES OF POLYMERIZED SBO SAMPLES

Viscosity, A.V., Free

Polymerized Pa.s at mg Iodine Monomer, Oligomers, fatty
SBO 25 8C KOH/g value Mn Mw Mw/Mn % % acids, %

OSO-4 5.34 5.3 76.3 2410 10530 4.36 28.3 70.4 1.18
OSO-5 7.84 4.4 73.6 2500 15500 6.20 26.0 73.2 0.78
OSO-6 10.45 3.3 66.6 2540 20800 8.18 24.5 74.5 0.76
OSO-8 18.50 4.2 65.2 2570 23900 9.29 24.7 74.4 0.81

at 5–40 phr of EPDM rubber cured with peroxides, comparable effects on processing and properties
were obtained.3
In this article, we have tested the effect of four polymerized SBO of high viscosity on
processing and physical properties of EPDM rubber in a standard sulfur-cured formulation. The
rational for using high-molecular-weight oil is based on the assumption that although compatibility
may decrease with increasing molecular weight, the chance of oil being chemically bonded to
rubber increases with molecular weight, and diffusion (sweating out) would be less likely.
Separately, the effect of sulfur concentration on properties was studied. EPDM-1 (paraffinic oil)
and EPDM-6 (pure SBO) were reference samples, while EPDM-2 to EPDM-5 were prepared with
polymerized SBO of increasing molecular weight and EPDM-7 to EPDM-10 with varying sulfur
content. Polymerized oils were prepared by methods described previously.7,8

EXPERIMENTAL
MATERIALS

Refined, bleached, and deodorized SBO used in this work had an iodine value of 130, viscosity
of 0.06 Pa.s, and molecular weight about 874. Sunpar 2280 is a paraffinic oil with viscosity about
0.4 Pa.s at 40 8C and was used as a reference. Large quantities of polymeric SBO were prepared via
cationic polymerization to desired molecular weight and viscosities. Characteristic properties of
polymerized SBO samples are listed in Table I.
Ten different EPDM rubbers were prepared with 50 parts per hundred parts of rubber (phr) of
paraffinic oil (control compound 1) and 50 phr of pure SBO (EPDM-6), whereas others contained
50 phr of one of four polymerized SBO. The standard sulfur-based EPDM curing agent is used at 1.5
phr of sulfur. In addition, a new series of compounds filled with 50 phr of polymerized oil (which
displayed the best properties) were made with varied concentration of sulfur (1.5, 2.0, 2.5, and 3.0
phr) and one with an increased accelerator level. Sample formulations and designations are given in
Table II.

METHODS

Differential scanning calorimeter (DSC) model Q100, from TA Instruments (New Castle, DE,
USA) was used for studying temperature transitions of rubber compounds. Measurements were
performed at a heating rate of 10 8C/min from 80 8C to 200 8C in nitrogen.
Thermogravimetric analyzer model Q50 (TA Instruments) was used for examining the thermal
stability of EPDM rubber compounds. All experiments were carried out under nitrogen at the
heating rate of 10 8C/min, from 25 8C to 600 8C.
 TABLE II
EPDM COMPOUNDS FORMULATIONS

First cycle EPDM -1 EPDM -2 EPDM -3 EPDM -4 EPDM -5 EPDM -6 EPDM-7 EPDM-8 EPDM-9 EPDM-10

Ingredient
VISTALON 6505 100 100 100 100 100 100 100 100 100 100
ZINC OXIDE 5 5 5 5 5 5 5 5 5 5
STEARIC ACID 1 1 1 1 1 1 1 1 1 1
AFLUX 42 2 2 2 2 2 2 2 2 2 2
TMQ 1 1 1 1 1 1 1 1 1 1
N550 black 100 100 100 100 100 100 100 100 100 100
SUNPAR 2280 50
OSO-4 50 50 50
OSO-5 50
OSO-6 50 50 50
OSO-8 50
Soybean oil 50
Second cycle
Sulfur 1.5 1.5 1.5 1.5 1.5 1.5 2.0 2.5 3.0 1.5
TMTD 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 4.0
MBT 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
EPDM RUBBER PLASTICIZED WITH POLYMERIC SOYBEAN OIL
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Thermomechanical analyzer (TMA) model Q400 (TA Instruments) was used for examining
thermal expansion of EPDM rubbers. All experiments were carried out under nitrogen with the
heating rate of 5 8C/min from 90 8C to 100 8C.
Dynamic mechanical tests were carried out on DMA 2980 from TA Instruments at 10 Hz and at
a heating rate of 3 8C/min in a temperature range from 90 8C to 100 8C.
Elastic recovery at 50%, 100%, and 200% deformation was studied on the Q-Test 2 tensile
tester from MTS (Eden Prairie, MN, USA). Specimen sizes were 7 mm 3 2 mm 3 50 mm (gauge
length was 50 mm). The extension rate was 50 mm/min (i.e., 100%/min).
Equilibrium swelling and Soxhlet extraction were carried out in toluene.
Processing properties and cure characteristics were measured on a moving die rheometer
(MDR) at a cure temperature of 163 8C.
Other physical and dynamic properties were measured using the following ASTM methods:

Hardness: ASTM D 2240 Shore A

Tensile, elongation, and modulus: ASTM D 412 Method A
Tear test Die C: ASTM D 624
Compression set: ASTM D 395 Method B
Oven age: ASTM D573
Dynamic properties: ASTM D5992: G’ and tan delta were tested at 610% shear strain, 10 Hz,
21 8C using double lap shear specimens. Static modulus G is a 25% secant modulus, also
tested at 21 8C.

RESULTS AND DISCUSSION

Extender oils must be miscible with rubber in order to serve their purpose. Solubility depends
on the chemical structure, but as with all polymers, it is governed by enthalpic and entropic forces.
Generally, two materials are miscible if free energy of mixing DG¼DHTDS is ,0. A simplified
approach when one component is a solvent of low molecular weight is based on the enthalpy factor
alone, where two materials are miscible when their solubility parameters, d, are close enough,
usually d1  d2 , 4 if units are MPa1/2. The estimated solubility parameter for SBO is about 17
MPa1/2.9 The solubility parameter of EPDM rubber was estimated as 17. 1 MPa1/2.10 The Hansen
solubility parameter for low Mooney unvulcanized EPDM is about 17.5.11 The solubility parameter
of paraffinic oil was reported as d¼15.3 MPa1/2, which is somewhat lower but close enough to d for
SBO.12 When polymerized, SBO reduces solution power because of the influence of the entropic
factor, although the solubility parameter is virtually unchanged. However, higher-molecular-
weight additives display slower diffusion, and if copolymerized with the rubber, they create an
internal permanent plasticizer. It is interesting that when swelling the EPDM rubber in a range of
solvents, it was found that regardless of the solubility parameters, polarity, dielectric constants,
acidity, or basicity of solvents, a linear relationship existed between molar volume V1 and the
number of moles of solvent in the gels, n1. With an increase of V1, n1 decreases.13 Although the
predictive power of the solubility parameter is rather limited in complex filled systems such as
rubber, the analysis shows that SBO should display a good miscibility with EPDM rubbers.

PROCESSING, PHYSICAL, AND DYNAMIC PROPERTIES

Rheological, physical, and dynamic properties of EPDM compounds were carried out in
industrial conditions at Lord Corporation using standard rubber testing equipment. Table III
displays rheological, physical, and dynamic properties of rubbers. The EPDM compounds were
 TABLE 3
RHEOLOGICAL, PHYSICAL, AND DYNAMIC PROPERTIES OF EPDM COMPOUNDS

Property EPDM -1 EPDM -2 EPDM -3 EPDM -4 EPDM -5 EPDM -6 EPDM-7 EPDM-8 EPDM-9 EPDM-10

Rheometer at 163 8C
ML Low torque, dN-m 1.69 1.92 1.92 2.03 2.14 1.77 1.77 1.82 1.65 1.62
MH High torque, dN-m 19.55 16.38 13.33 15.14 13.90 4.99 13.51 15.26 18.03 15.16
Tc(95), min 7.7 17.2 19.1 17.7 16.7 4.5 16.6 16.6 15.0 15.3
Ts(2), min 1.0 1.0 1.3 1.1 1.3 3.1 1.1 0.9 0.8 1.2
Physical properties
Hardness, Shore A 71 72 70 70 70 59 74 75 78 75
Tensile, MPa 13.1 9.31 8.2 8.6 8.17 1.64 9.06 9.17 10.4 8.73
Elongation, %) 373 496 450 480 414 661 415 394 430 487
100% modulus 736 513 448 479 466 174 513 596 658 508
Tear die C, PPI 159 192 171 189 168 126 177 176 181 189
Compression set
70 h at 150 8C 65.9 80.9 84.1 82.0 82.7 112.4 101.5 99.2 97.7 101.5
Oven age 70 h at 150 8C
Hardness, pts 78 80 79 80 81 77 85 87 87 85
Tensile, MPa 13.2 12.6 11.87 12.0 11.96 8.0 11.5 11.8 12.2 11.2
Elongation, % 161 185 201 200 192 45 89 86 66 102
Change in hardness, pts 7 8 9 10 11 18 11 12 9 10
Change in tensile, % 0.6 35.6 44.7 39.9 46.3 389.5 27.2 29.2 17.1 27.9
Change in elongation, % -56.8 -62.7 -55.3 -58.3 -53.6 -93.2 -78.6 -78.2 -84.7 -79.1
TL-440: 039A at 21 8C
G’10/10, MPa 2.68 3.16 2.80 3.00 2.93 1.60 2.95 3.00 3.27 3.00
Tan delta 10/10 0.279 0.273 0.269 0.274 0.263 0.270 0.275 0.274 0.259 0.279
EPDM RUBBER PLASTICIZED WITH POLYMERIC SOYBEAN OIL

25% static G, MPa 1.96 1.49 1.75 1.85 1.70 0.93 1.75 1.92 2.27 1.84
Dynamic/static ratio 1.37 1.69 1.60 1.62 1.72 1.72 1.69 1.57 1.44 1.63
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FIG. 1. — Bleed-out of soybean oil from cured tensile pad molded from EPDM-6.

prepared in a BR1600 Lab Banbury mixer with final dispersion accomplished by milling on a 15 cm
3 30 cm two-roll mill. Processing properties and cure characteristics are measured on an MDR at a
cure temperature of 163 8C. Despite close solubility parameters, SBO is not fully compatible with
EPDM rubber at 50 phr because the oily surface of sample EPDM-6 indicated that SBO bleeds out
after cure (Figure 1).
Wang et al.14 studied the effect of transgenic SBO (TSO) on properties of EPDM rubber. The
results showed that TSO has a better plasticization effect than paraffinic oil on EPDM. In addition,
the curing characteristics of the EPDM compounds were studied. TSO was found to react with the
curing agent dicumyl peroxide (DCP) during the curing process. Excessive amounts of TSO led to
low crosslinking density, which was improved by adjusting the added amount of DCP.
The rheometer measures the progress of cure at a given temperature as a function of time. The
low torque ML measures the minimum viscosity of the compound, whereas the high torque
measures the equilibrium maximum torque at the completion of cure. Ts(2) or scorch time is the
time at which the rubber has increased to two torque units above the minimum torque (ML) and
gives an indication of how quickly the inception of cure begins. Tc(2) was similar for all compounds
except for EPDM-6 containing the SBO. This shows there is significant retardation of the cure when
using SBO. Rheology data show that polymerized SBO does not reduce the viscosity of the rubber
as much as the paraffinic oil. This is not surprising because the paraffinic oil has measurably lower
viscosity than the polymerized SBO. The pure SBO reduced the viscosity of the rubber even further,
but bleed out of the oil shows that it is incompatible at a level of 50 phr.
It is typical to consider the technical cure time to be the time at which the compound achieves
either 90% (T90) or 95% (T95) of the difference between the ML and MH value. We chose Tc(95)
as the ideal cure time. The extreme reduction in high torque and tensile strength combined with the
high compression set suggest that the pure SBO in EPDM-6 interfered with the cure as well. The
time required to reach 95% of total cure is affected by the type of plasticizer. For the compound
EPDM-1, extended with paraffinic oil, the cure time Tc95 is 7.7 min, whereas for compounds
extended with polymerized oil, the Tc95 is more than double, in the range from 16.7 to 19.1 min.
SBO triglycerides are mixtures of fatty acids including alpha-linolenic acid, linoleic acid, oleic acid,
 EPDM RUBBER PLASTICIZED WITH POLYMERIC SOYBEAN OIL 673

stearic acid, and palmitic acid. It is known that acidic ingredients can retard a sulfur cure, and it is
likely that at 50 phr, the level of acid is sufficient to cause the observed cure retardation.
Changing the sulfur level from 1.5 to 2.0 to 2.5 phr (EPDM-2, EPDM-7, EPDM-8) showed
minimal impact on properties except for compression set. As is often the case with EPDM, more
sulfur increases the compression set. Doubling the sulfur from 1.5 to 3.0 phr (EPDM-4, EPDM-9)
shows a moderate increase in tensile strength and modulus with a slight decrease in elongation. The
increase in hardness and modulus coupled with the decrease in elongation shows that additional
sulfur increases crosslink density. Additional accelerator reduces cure time (EPDM-4 vs. EPDM-
10), but it still causes an increase in compression set. Again, the increase in hardness and modulus
coupled with the decrease in elongation shows that additional sulfur increases crosslink density. An
increase in crosslink density normally improves compression set. It is not understood why the
opposite effect was observed in this case.
Li et al.15 studied properties of SBR extended with SBO and dicyclopentadiene (DCPD)
modified SBO (MSO). DCPD has more reactive double bonds than vegetable oils. They found that
the decrease in the crosslink density of the sulfur-cured SBR/SBO and various SBR/MSO
vulcanizates is due to the reaction of the SBO and MSO with the curatives. The oil altered the
crosslink structure, resulting in a large improvement in product properties. The SBR/SBO
compound and its vulcanizate exhibited the lowest Tg, leading to better low-temperature properties.
Mechanical properties including hardness, tensile strength, elongation and 100% modulus,
tear die C, and compression set are measured before and after oven aging. Hardness was about 70
Shore A in all samples except in EPDM-6 extended with pure SBO and increased in samples cured
with additional sulfur (EPDM-7, -8, and -9). The highest tensile strength of 13.1 MPa was observed
in the rubber extended with mineral oil and very low (1.6 MPa) in EPDM extended with pure SBO.
Tensile strengths of rubbers with polymeric SBO were about 8.5 MPa and were not significantly
affected by the molecular weight of oils, but they increased slightly with increasing sulfur content.
Evidently, EPDM rubbers extended with polymerized SBO have better property retention than that
extended with pure SBO.
Elongation at break was higher in samples with lower tensile strength, being around 30%
higher in EPDM extended with polymerized SBO than in EPDM-1, but pure SBO showed almost
80% higher value than the mineral oil–extended sample. Rubbers extended with polymerized oil
show superior tear strength than the mineral oil–extended sample and particularly higher than pure
SBO extended rubber, but no clear effect of molecular weight and sulfur content was observed.
Vegetable oils consistently gave higher compression set results than paraffinic oil. Oven aging for
70 h at 150 8C increased hardness and slightly increased tensile strength but dramatically decreased
elongation. These results are consistent with higher crosslinking density of mineral oil–extended
EPDM than in samples with polymerized oil. It appears that all sulfur in mineral oil extended
formulation goes toward formation of crosslinks between rubber chains, whereas some sulfur in oil-
extended EPDM is used to attach oil molecules to rubber or increase molecular weight of oils.
Dynamic properties, G 0 and tan d, were tested at 610% shear strain, 10 Hz, at 21 8C. Dynamic
modulus is higher in compounds extended with polymerized SBO, whereas damping properties as
measured by tan d are very similar. The dynamic/static ratio for compounds extended with
polymerized SBO is somewhat higher (1.60-1.72) than in the control EPDM extended with
paraffinic oil (1.37), but the increased sulfur content did not show significant effect.

THERMAL PROPERTIES OF EPDM RUBBERS

Rubber compounds are complex, multicomponent systems, which are reflected on their
complex DSC curves. DSC traces (Figure 2) show the same glass transition of EPDM rubber
compounds extended with polymerized SBO as with paraffinic oil at about52.5 8C. Thus, neither
674 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 90, No. 4, pp. 667–682 (2017)

FIG. 2. — DSC traces for EPDM rubbers extended with polymerized SBO (EPDM-1 is extended with paraffinic oil, EPDM-
6 is extended with pure SBO).

additional amount of curing agent nor molecular weight of oil affected Tg. The exception was the
sample with pure SBO (EPDM-6) with Tg at 54.7 8C. Thus, SBO was a stronger plasticizer for
EPDM than other oils despite the fact that it showed limited miscibility and bleed out. Sulfur
concentration also did not have a significant effect on Tg. Broad endotherm at 13 to 17 8C was
tentatively ascribed to the melting of fatty acids in oils. It slightly increased with increasing
molecular weight of oils.
The TMA of rubber compounds is carried out in the expansion mode (Figure 3). The glass
transition temperature is observed as a change of slope on the dimension change versus temperature
curves. Tg values obtained from TMA are somewhat higher than ones obtained by DSC. Linear
coefficients of thermal expansion (LCTE) at several temperatures are listed in Table IV. In the

FIG. 3. — Dimension change as a function of temperature for EPDM compounds.

 EPDM RUBBER PLASTICIZED WITH POLYMERIC SOYBEAN OIL 675

TABLE IV
LINEAR COEFFICIENT OF THERMAL EXPANSION OF EPDM RUBBER COMPOUNDS AT DIFFERENT TEMPERATURES

Sample a at 70 8C a at 20 8C a at 0 8C a at 25 8C a at 50 8C a at 75 8C

EPDM-1 58 159 158 142 136 149

EPDM-2 64 178 162 124 89 110
EPDM-3 68 158 160 136 99 107
EPDM-4 78 155 176 156 131 134
EPDM-5 75 142 169 157 127 118
EPDM-6 64 207 214 184 157 166
EPDM-7 64 149 155 132 118 111
EPDM-8 71 136 141 127 103 105
EPDM-9 67 142 161 147 155 150
EPDM-10 68 135 136 130 134 124

glassy region, LCTE is in the range of 58–78 lm/m8C, being the smallest for the EPDM rubber
extended with paraffinic oil. In the rubbery state, the average LCTE at 0 8C was 163 lm/m8C; at
room temperature, it was around 144 lm/m8C and above 50 8C decreased to 125 lm/m8C. The
highest LCTE was found for the sample extended with pure SBO. The addition of sulfur does not
show a clear effect on glass transition. LCTE in the glassy and rubbery state varied irregularly with
increasing molecular weight and temperature. However, LCTE values in the rubbery state were
lower than typical LCTE of about 250 lm/m8C for amorphous thermoplastics in the rubbery state.
Dynamic mechanical properties are displayed in Figures 4 and 5. Storage modulus (E 0 ) curves
for compounds extended with polymerized SBO (Figure 4) show similar shapes, but small
differences are observed in the rubbery region, where higher moduli were observed with systems
crosslinked with higher sulfur content. E 0 values varied from 3.64 to 4.28 GPa in the glassy region
and between 12.1 MPa for EPDM-5 and 20.7 MPa for EPDM-9 in the rubbery state. EPDM-6,
extended with pure SBO, displayed lower storage modulus in the entire temperature range,
indicating a stronger plasticizing effect than with other oils.

FIG. 4. — Storage modulus versus temperature for EPDM rubber compounds.

676 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 90, No. 4, pp. 667–682 (2017)

FIG. 5. — Tan delta versus temperature for EPDM rubber compounds.

Tan d temperature curves (Figure 5) display an a-relaxation peak around 35 8C associated
with Tg and b-relaxation below90 8C, except for the samples with pure SBO and paraffinic oil, for
which a weak b-peak was observed at about 65 8C. The tan d maximum of about 0.5 indicates
fairly good damping properties of these rubbers, which were formulated for dynamic applications.
In the rubbery region, the highest tan delta was observed in the rubber plasticized with pure SBO
(~0.2), somewhat lower in those with polymerized SBO, and the lowest with EPDM-1.
Glass transition temperature (a-relaxation) of all samples is determined from the loss modulus
peak (not shown here). Table V lists glass transition temperatures determined by three methods
(DSC, dynamic mechanical analysis [DMA], and TMA). Higher values for Tg from DMA are due to
the effect of frequency.
Elastic recovery of EPDM compounds was determined at three deformations: 50%, 100%, and
200% (during three cycles). Figure 6 illustrates stress–strain hysteresis for EPDM-9 at 200%
deformation. The initial high stress in the first cycle of deformation is significantly reduced in the
second and third cycle due to stress softening (Mullins effect).16 Elastic recovery, however, does

TABLE V
GLASS TRANSITION TEMPERATURES OF EPDM RUBBERS OBTAINED BY THREE
METHODS

Sample Tg (DSC) Tg (DMA) Tg (TMA)

EPDM-1 52.4 33.6 44.5

EPDM-2 51.8 35.3 47.6
EPDM-3 52.9 35.2 45.0
EPDM-4 52.4 34.2 43.3
EPDM-5 51.8 34.6 43.5
EPDM-6 54.7 39.4 46.3
EPDM-7 52.5 34.4 42.5
EPDM-8 52.2 32.9 43.6
EPDM-9 52.0 34.0 43.9
EPDM-10 52.1 34.9 49.1
 EPDM RUBBER PLASTICIZED WITH POLYMERIC SOYBEAN OIL 677

FIG. 6. — Stress–strain hysteresis curves for EPDM-9 at 200% elongation.

not change in subsequent cycles. Similar curves are obtained for all samples. Elastic recovery
values after the first cycle of deformation for all samples and at all three deformations are plotted in
Figure 7. The highest elastic recovery was observed with the rubber extended with paraffinic oil and
the lowest with pure SBO. Some samples extended with polymerized oil (EPDM-2, EPDM-4)
display good elasticity at low deformation but have poor response at higher deformations. Sample
EPDM-9 displays the highest elastic recovery of all samples extended with polymerized SBO, as a
consequence of additional sulfur (higher crosslinking). Modulus in rubbers is often presented as
stress at a certain deformation, which was taken from elastic recovery curves as maximum stress at a

FIG. 7. — Elastic recovery of EPDM rubbers after first cycle at 50%, 100%, and 200% elongation.
678 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 90, No. 4, pp. 667–682 (2017)

FIG. 8. — Maximum stress for EPDM rubbers after the first cycle, at 50%, 100%, and 200% elongation.

given elongation. The highest maximum stress (Figure 8) was observed in the sample extended with
paraffinic oil followed by EPDM-8 and -9 with increased sulfur content. This proves the higher
plasticizing power of polymerized oils than that of paraffinic oil. The lowest modulus (maximum
stress) was found in the compound extended with pure SBO due to the strongest plasticizing effect.

SWELLING AND SOLVENT EXTRACTION

Equilibrium swelling of EPDM compounds was carried out in toluene at room temperature for
72 h. The sample size was in the range of 1.1 to 1.2 g. Figure 9 displays the change of swelling ratio
(w/w0) with swelling time. It is clear that EPDM-6 (extended with SBO) has the highest tendency to
swell in toluene (swelling ratio was 3.8), whereas at the other end is compound EPDM-1 extended
with paraffinic oil, which showed a swelling ratio of only 1.7. In between are EPDM rubbers
extended with polymerized SBO, having an average swelling ratio of 2.4 after 72 h of swelling.
Another observation is concerned with time to reach equilibrium. EPDM-1 compound reached
equilibrium swelling already after 2 h; for compounds extended with polymerized SBO, it took
about 4 h to reach equilibrium, and the compound extended with SBO continued to swell in the first
24 h. After 72 h of swelling, samples were transferred into pans and dried until constant weight and
sol fraction, Ws (%), was calculated based on the following equation:
ðw0  wg Þ
Ws ¼ 3 100
w0
where w0 is the weight of sample before and wg is the weight of sample after swelling and extraction.
The oil content in the EPDM compound is about 19% (note that some additives are also extractable
from the compounds). Sample EPDM-6 (Figure 10), extended with pure SBO, has the highest sol
fraction (SBO is not compatible with EPDM matrix and oil bleeds out). Paraffinic oil was also
extracted from the compound (EPDM-1) after swelling in toluene. Compounds extended with
EPDM RUBBER PLASTICIZED WITH POLYMERIC SOYBEAN OIL 679

FIG. 9. — Equilibrium swelling ratio for EPDM rubbers after swelling in toluene for 72 h.

FIG. 10. — Sol fraction of EPDM compound by two methods.

680 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 90, No. 4, pp. 667–682 (2017)

FIG. 11. — Weight loss as function of temperature of EPDM rubber compounds.

polymerized SBO have a sol fraction in the range from 8.6% for EPDM-9 to 12.1% for EPDM-3,
indicating that polymerized SBO is probably co-cured with rubber to a certain extent through
double bonds. Comparison of samples EPDM-2 (1.5 phr sulfur), EPDM-7 (2 phr sulfur), and
EPDM-8 (3 phr sulfur; all three extended with OSO-4) shows a slight decrease of sol fraction from
11% for EPDM-2 to 10.2% for EPDM-8. A more significant change in sol fraction is observed in
samples EPDM-4 (1.5 phr sulfur, OSO-6) versus EPDM-9 (3 phr sulfur, OSO-6), where Ws
changed from 11% to 8.6%. These two observations are additional proof that the addition of sulfur
plays a role in the co-curing reaction. Now, when compared with EPDM-4 (1.5 phr sulfur, 3 phr
accelerator) and EPDM-10 (1.5% sulfur, 4 phr accelerator), the sol fraction increases slightly from
11% to 11.5%.
Soxhlet extraction was carried out under the reflux of toluene for 48 h. The sample size was
about 0.6 g. After 48 h of swelling, samples were dried to the constant weight, and sol fraction, Ws
(%), was calculated using Eq. 1. Figure 10 displays the sol fraction for EPDM compounds by
Soxhlet extraction and equilibrium swelling. The Soxhlet extraction method is more efficient than
equilibrium swelling (difference of about 15%). The total amount of plasticizer in the compound is
about 19%; additives that are also extractable sum up to about 22–23%, meaning that about 50% of
polymerized SBO is co-cured in the rubber. It is clear that paraffinic oil and pure SBO are
completely extracted (EPDM-1 and EPDM-6). In samples in which polymerized SBO was used,
the sol fraction was way below the total amount of oil in the compounds (,19%), meaning that part
of the oil is bonded with EPDM matrix. In addition, the increased amount of sulfur promoted co-
curing of polymerized SBO, observed as even lower sol fraction in samples EPDM-7, EPDM-8,
and EPDM-9.

THERMAL STABILITY OF EPDM RUBBERS

TGA and derivative TGA (DTGA) were employed to measure weight loss and the rate of
weight loss of rubbers as shown in Figures 11 and 12. Table III summarizes characteristic
degradation temperatures and corresponding weight losses. TGA shows three characteristic steps
of degradation of EPDM compounds extended with polymerized SBO. Onset of the weight loss
appears at about 155–160 8C, and the first maximum on DTGA curves observed at about 210 8C is
 EPDM RUBBER PLASTICIZED WITH POLYMERIC SOYBEAN OIL 681

FIG. 12. — Derivative weight loss as a function of temperature for EPDM compounds.

associated with a loss of about 1.1%. The first major degradation step appears at about 393 8C due to
the oil degradation and is followed by polymer chains scission at about 460 8C. Total weight loss in
all samples is about 60%, with the residue being the filler.

CONCLUSIONS
 Replacement of paraffinic oil with bio-based plasticizer, polymerized SBO of different
molecular weights, as well as pure SBO was studied.
 Pure SBO showed the strongest plasticizing effect but also exhibited incomplete miscibility
with EPDM at 50 phr. It decreased tensile strength, hardness, and modulus and increased
elongation and compression set more than any oil.
 Polymerized SBO have good compatibility with EPDM rubber matrix. They show
decreased tensile strength and modulus but increased elongation, tear strength, and
compression set when compared with paraffinic extender.
 The presence of double bonds in polymerized SBO can lead to co-curing of polymerized oil
with the rubber matrix, but they also lower cross-link density of EPDM more than with
paraffinic oil.
 Adjustment of compound formulation with addition of sulfur content is recommended to
obtain optimal product properties.
 Substitution of polymerized SBO is unlikely to be successful in applications requiring low
compression set.
 The molecular weight of the polymerized oils did not have a clear effect on properties,
possibly because the molecular weight differences were not large enough.

ACKNOWLEDGEMENT
The authors are indebted to United Soybean Board for funding this project.
682 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 90, No. 4, pp. 667–682 (2017)

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[Received January 2017, Revised June 2017]