ROHSTOFFE UND ANWENDUNGEN
RAW MATERIALS AND APPLICATIONS
Hazelnut oil ⋅ epoxidized hazelnut oil ⋅
low temperature flexibility ⋅ oil swel-
ling ⋅ plasticizer
In this study, the use of hazelnut oil
(HaO) and epoxidized hazelnut oil
(EHaO) as plasticizers in acrylonitrile
butadiene rubber (NBR) and polychloro-
prene rubber (CR) was investigated.
Tensile properties, glass transition tem-
peratures, swelling charasteristics in
polar liquids of the compounds of HaO
and EHaO were determined. Oil swel-
ling performance was better with EHaO
and not more than 17 % swelling was
reached when NBR rubber was used.
While reaching these values, tensile
properties were acceptable.
Einsatz von Haselnussöl und
epoxidiertem Haselnussöl als
Weichmacher für NBR und CR
Haselnussöl ⋅ epoxidiertes Haselnussöl ⋅
Tieftemperaturflexibilität ⋅ Ölquellung ⋅
Weichmacher
In dieser Arbeit wird der Einsatz von
Haselnussöl und expoxidiertem Hasel-
nussöl als Weichmacher für NBR und
CR untersucht. Die Zug-Dehnungsei-
genschaften, Glasübergangstempera-
tur, Quellungcharakteristiken in polaren
Flüssigkeiten wurden für die entspre-
chenden Vulkanisate untersucht. Mit
EhaO war die Ölquellung bei NBR mit
17% niedrig, wobei die Zug-Dehnungs-
eigenschaften befriedigend waren.
Figures and Tables:
By a kind approval of the authors
Author
Kemal Karadeniz, Neşe Ergüler,
Sakarya (Turkey)
Corresponding author
Kemal Karadeniz
Sakarya University
Department of Chemistry
Faculty of Science and Literat
54187 Sakarya, Turkey
kkaradeniz@sakarya.edu.tr
www.kgk-rubberpoint.de
Investigation of Plasticizer Effect
of Hazelnut Oil and its Epoxi-
dized Derivative on Chloroprene
and Nitrile Rubbers
The use of plasticizers to extend and sof-
ten the rubbers is a well-known tech-
nique. Many general purpose rubbers or
speciality rubbers such as nitriles, neopre-
ne, polyurethanes, polyacrylates and chlo-
rinated polyethylene necessitate the use
of plasticizers due to some problem might
arise. General purpose rubbers are prefer-
red mostly because of their better high
temperature performance, better oil and
solvent resistance, better aging characte-
ristics or physical properties in spite of
their high cost[1]. The polar groups on the
polymer backbone are responsible for
these required charasteristics.
Although these polar groups improve
the hydrocarbon solvent resistance and
high temperature performance of the
rubber, they also exert undesirable side
effects on the low temperature proper-
ties including increased glass-transition
temperature and polymer brittleness[2].
Many plasticizers are used to extend
and soften the rubber in order to aid the
processing or to lower the cost of rubber
compounds. It is known that, polarity, aro-
maticity, molecular weight and volatility
are the significant parameters affecting
the properties of plasticizers. Polarity of
the plasticizer is particularly important
when speciality rubbers containing polar
groups are involved as the solubility para-
meters of the plasticizer and the rubber
need to be compatible. The polar groups
that commonly exist in plasticizers involve
halogens, nitriles, ethers, esters and ure-
thanes[3]. High aromaticity favors compa-
tibility and lowers volatility but high mole-
cular weight compounds generally exert
lowered compatibility and tend to bleed
out of a particular system at higher tem-
peratures[4]. Although a variety of plasti-
cizers have been used in formulations
with speciality rubbers[5], desirable low
temperature properties, resistance to ext-
raction by solvents and low volatility are
not met to the maximum required level.
Phthalate plasticizers, mostly bis-(2-ethyl-
hexyl) phthalate (DEHP or DOP), dibutyl
phthalate (DBP) and benzyl butyl phthala-
te (BBP) are widely used as general-purpo-
se ester plasticizers because of their low
cost and high volume[6]. They are also re-
ferred as commodity plasticizers. Plastici-
zers other than phthalates are generally
referred as speciality plasticizers. These
plasticizers may also be used alone in the
compound. The primary purpose for the
use of speciality plasticizers in the com-
pound is the performance properties not
achievable with phthalate esters. Besides
using plasticizers, blending at least two
different elastomers to have optimum low
temperature and oil resistance perfor-
mance which can not be obtained from
each of these elastomers has long been
employed. One example is a blend of acry-
lonitrile-butadiene rubber (NBR) wih a low
polarity rubber such as styrene-butadiene
rubber (SBR), or butadiene rubber (BR).
Due to their exudation to atmosphere,
toxic impact on environment and non-
biodegradability, in recent years, phthala-
te esters, particularly bis-(2-ethyl-hexyl)
phthalate (DEHP), were added on the list
of carcinogenic chemical substances by Eu
Substance Directive 67/5487 EEC[7, 8, 9].
As a result of these concerns, intensive
research on safer plasticizers has been ini-
tiated and alternative plasticizers other
than phthalates have been developed[10].
One of these alternatives is vegetable oils
as plasticizers [11]. The advantages of
using vegetable oils as plasticizers are their
higher molecular weights, high flash
points, lower volatility and compatibility
with many polymers [12, 13]. Depending
on the application, vegetable oils can be
used as plasticizers either “as is” or with
chemical modification. One one of these
modifications is to enhance their oxidative
stability which is one of disadvantages of
these oils. Epoxidation of double bounds
on fatty acid chain is the one of the chemi-
cal modifications [14] which results in sig-
nificant improvement of their lubricity and
thermal stability.[15,16]. Epoxidized vege-
table oils find various applications in many
areas of industry as an alternative to
phthalate plasticizers [17-18].
In this work, plasticizer effect of hazel-
nut oil (HaO) on compounds of NBR and
KGK · 10 2012 49
 ROHSTOFFE UND ANWENDUNGEN
RAW MATERIALS AND APPLICATIONS

CR rubbers was investigated. In addition,
HaO was epoxidized for the first time and
this epoxidation was confirmed by FTIR
and 1HNMR spectroscopy. Plasticizing ef-
fect of this epoxidized HaO (EHaO) on
subject compounds was also studied. The
impact of these oils on physical proper-
ties, low temperature and oil resistance
performance of the compounds were
measured and it was observed that these
properties was significantly affected.
Experimental
ping reached to 105-115 °C. The master-
batches were sheeted out at a laboratory
two-roll mill and aged for 4 h. Sulphur and
accelerator were then added to the aged
masterbatch and mixed using the two roll
mill for the final mix.
Characterization
Fourier Transform Infrared (FTIR) and
Nuclear Magnetic Resonance (NMR)
Spectroscopy
Epoxidation of hazelnut oil was confir-
med by FTIR and 1H-NMR spectroscopy.
FTIR spectra were recorded on a Schi-
madzu IR prestige -21 spectrophotometer
equipped with ATR device having a dia-
mond crystal, in a scanning range 650-
4000 cm-1 for 25 scans at a spectral resolu-
tion of 4 cm-1. Data were collected and
processed using IR solution software.
1H NMR spectra were recorded using
SHIMADZU Prestige-21 (200VCE) spec-
trophotometer operating at 300 MHz.
For data collection and processing, VN-
MR 6.1 C software was used.

Materials 1 Materials and suppliers

The materials used in this study are gi- Material Suppliers
ven in Table 1. Acrylonitrile-butadiene rubber (NBR)ACN33% Polimeri Europe
Polychloroprene rubber (CR) Denka
Epoxidation of hazelnut oil
Virgine hazelnut oil Ordu Yağ Sanayii A.Ş.
HaO which was produced by cold pressing
and without adding any antioxidant, was Carbonblack , SRF N772 Degussa
epoxidized according to the procedure re- Carbonblack, FEF N550, Alexandria
ported in literature [19]. A solution of hazel- Stearic acid Pt Musim Mass
nut oil (100g, 0,14 mole), glacial acetic acid Zinc oxide Metal Oksit, Turkey
(25,2 g, 0,42 mole), amberlite (25 g) and Soluble sulphur Flexsys
toluene (40 g) were heated to a constant Accelerator, N-Cyclohexyl-2-benzothiazole Flexsys
temperature of 55 °C by stirring in a four sulfenamide (CBS)
necked round bottomflask equipped with a Antioxidant, polymerized 1,2- dihydro-2,2,4 trimethyl Flexsys
thermometer, a stirrer and a reflux conden- quinoline (TMQ)
ser. Then, 30% H2O2 (79,4 g, 0,7 mole) was IRM 903, reference oil R.E.Carrol, inc.
added slowly from a addition funnel and Glacial acetic acid Merck KGaA, Germany
allowed to react at 55 °C for 7 hrs. Upon H 2O 2 Merck KGaA, Germany
completion of the reaction, the solution
Toluene Tekkim, Turkey
was filtered and washed with distilled wa-
Amberlite Sigma-Aldrich
ter to pH 7.0. The oil phase was dried with
anhydrous sodium sulfate and then filtered. Sodium sulfate Tekkim, Turkey
Finally toluene was removed in a vacuum
oven at 80 oC, 91 % yield was achieved. 2 HaO and EHaO loading of formulations in phr*
Formüla no 1 2 3 4 5 6
Compound mixing CR group
12 rubber formulations with CR rubber, 8
HaO 0 10 20 30 40 50
formulations with NBR (ACN % 33) were
EHaO 0 10 20 30 40 50
prepared. One formulation was used for
control in both CR and NBR groups and NBR group
did not contain any HaO or EHaO; and in HaO 0 5 10 15
the other formulations HaO was used in EHaO 0 5 10 15
half of them in each rubber group and *: parts per hundread rubber
EHaO was used in the other half [Table 2].
Compound formulations of CR rubber 3 Compound formulation of CR group 4 Compound formulation of NBR group
group and NBR rubber group were shown Ingredient Loading (phr) Ingredient Loading (phr)
in Table 3 and Table 4 respectively.
CR rubber 100 NBR 100
Compound mixing was carried out in
two stages using a Laboratory Banbury SRF N 772 55 SRF N 772 55
mixer of 260 cm3 capacity (Midgate, David HaO, EHaO (0-50) FEF N 550 10
Bridge) and a laboratory mill. Masterbatch MgO 4 HaO, EHaO (0-20)
mixing was carried out by setting the tem-
Stearic acid 0.5 Stearic acid 1
perature control unit at 90 °C, the rotor
speed at 40 rpm and the ram pressure at ZnO 5 ZnO 5
3.5 kg/cm2. The mixer was initially charged TMQ 2 TMQ 2
with rubbers, chemicals and fillers, carbon ETU 0.5 Sulphur 2.4
black and oil were added after 15 seconds.
CBS 0.75 CBS 1.2
The temperature at the moment of drop-

50 KGK · 10 2012 www.kgk-rubberpoint.de

 ROHSTOFFE UND ANWENDUNGEN
RAW MATERIALS AND APPLICATIONS

1 Solutions were prepared with deute-

rated chloroform (CDCl3 99.8 atom % D)
at 15 % concentration by volume.

Physical properties
The green rubber compound was cured
at 150 °C for 18 minutes in a steam hea-
ted curing press using compression mol-
ding for physical property tests.
Dumbell shaped specimens were pun-
ched out from the molded sheets. Tensile
properties were measured on Alpha ten-
someter 2000 according to ASTM D 412-
51 (2006) and at a crosshead speed of
500 mm/min. The hardness was measu-
red on a shore A durometer according to
ASTM D 2240 (2005)
Tg’s of oils and rubber compounds we-
re measured using Mettler Toledo DSC1
Figure 1 – FTIR spectrum of HaO
200W. Approximately 3 mg of samples
were weighed in aluminium pans (40 µL)
2 and were subjected to cooling-heating
cycles from -90 °C to 25 °C at 10 °C min-1
under nitrogen of 50 mL min-1. flow rate.
For oil resistance measurement, ASTM
D 471-06 test procedure was followed.
IRM 903 reference oil, analytical and pre-
cision balance with density kit (Mettler
Toledo AB204-S) was used. Samples were
immersed in reference oil for 168 h at 100
0C and volume change was measured.

Results and Discussion

Epoxidation of hazelnut oil

Epoxidation of hazelnut oil was confirmed
by FTIR and 1HNMR spectroscopy. The ap-
pearance of epoxy absorbance band at
823 and 842 cm-1 on FTIR spectrum (Fig 1
and 2) shows the epoxy conversion[19].
In the 1H NMR spectum of EHaO (Figu-
Figure 2 – FTIR spectrum of EHaO
re 4), as compared to the spectrum of HaO

5 Physical properties of formulations of CR group

Phr yağ 00 10 20 30 40 50
HaO EHaO HaO EHaO HaO EHaO HaO EHaO HaO EHaO HaO EHaO
Hardness(Shore A) 75 - 65 62 60 57 50 48 45 40 37 35
Tensile strength (MPa) 17.52 - 14.78 13.32 14.05 10.04 13.68 8.45 12.65 7.71 12.01 5.43
Elastic modüle (%100) 8.72 - 3.32 1.58 3.12 1.45 2.51 1.39 1.84 1.35 1.58 0.91
Elongation at break 198.2 - 261.4 272.1 267.2 310.8 262.0 312.9 346 341.2 379 331.8

6 Physical properties of formulations of NBR group

Phr oil 00 5 10 15
HaO EHaO HaO EHaO HaO EHaO HaO EHaO
Hardness(Shore A) 76 - 70 72 67 69 64 60
Tensile Strength (MPa) 17.17 - 12.56 19.31 9.72 17.78 7.21 9.17
Elastic modüle (100 %) 4.14 - 3.62 4.89 3.02 4.42 2,92 3.39
Elongation at break (%) 212.3 - 236.40 339.10 246.30 357.40 296.40 394.40

www.kgk-rubberpoint.de KGK · 10 2012 51

 ROHSTOFFE UND ANWENDUNGEN
RAW MATERIALS AND APPLICATIONS

(Figure 3), new peaks corresponding to 3

the -CH- protons of the epoxy ring and –
CH2- protons alpha to the epoxy ring ap-
peared at δ= 2.8-3.2 ppm and δ= 1.4-1.6
ppm, respectively, which confirmed suc-
cessful epoxidation[20].

3.2 Physical properties

Tensile stress, shore hardness, elongati-
on at break, modulus 300 % of formulati-
ons are summarized in Table 5 and 6.
As expected, hardness of the formula-
tions of CR group decreased significantly
with increased oil while tensile strength
and 300 % modulus increased slightly. In-
crease at elongation at break is much
more smaller than tensile strength and
modulus [21]. Noticable point is that the
tensile strength of the compounds mixed
with EHaO was significantly lower than
the one mixed with HaO, especially at
higher oil loadings.
Figure 3 – 1HNMR spectrum of HaO
As for formulations of NBR group, hard-
ness, tensile strength and modulus 100 %
decreased with increased HaO and EHaO 4
loading while elongation at break increa-
sed. But, modulus and tensile strenght of
formulations prepared with EHaO increa-
sed with increased 5 and 10 phr of oil
loading at the begining and then decrea-
sed again in line with the literature[22].

Low temperature performance

The onset crystallization temperatures of
HaO and EHaO were measured by DSC
and was found 16.6 °C and 12.6 °C for HaO
and EHaO respectively. Thermograms of
HaO and EHaO are shown in Fig. 5 and Fig.
6. respectively. In line with the literature,
crystallization temperature shifted to a
higher temperature due to the increased
polarity of epoxy group compared to that
of the C=C double bounds [23,24]. The Tg
performance of formulations of CR group
are shown in Table 7.
Figure 4 – 1HNMR spectrum of EHaO
Tg’s decreased with increased HaO loa-

5 6

Figure 5 – DSC curves of HaO and EHaO Figure 6 – DSC curves of CR group formulations with lower HaO loading

52 KGK · 10 2012 www.kgk-rubberpoint.de

 ROHSTOFFE UND ANWENDUNGEN
RAW MATERIALS AND APPLICATIONS

dings of 10, 20, 30 phr while significant rubber compound from -37.6 °C to -
decreases were observed with loadings of 64.86 °C and – 66.86 °C for 40 and 50 phr
40 and 50 phr. The decreases can be attri- loadings of HaO, respectively is clear in-
buted to the interaction between double dication of plasticization effect. The sa-
bond on the HaO and chlorine atoms of CR. me effect was observed for EHaO after
As for EHaO, interactions mentioned above 30 phr loadings. DSC curves of CR formu-
disappered due to absence of double lations are shown in Fig 6, 7, 8 and 9.
bonds and hence decreases in Tg became The Tg of cured/filled NBR (33% ACN) is
higher than that of HaO. The decreases in -24 °C[25]. Therefore, there was no signifi-
Tg, that is, plasticization effect were noti- cant plastization effect of HaO since no
cable with loadings higher than 40 phr for significant decrease in Tg of NBR formula-
both HaO and EHaO. tions prepared with HaO was observed
The Tg of cured/filled rubber is -34 °C whereas the plastisizing effect was obser-
[25], the decrease in Tg of unplasticized ved in case of EHaO as a 3 °C drop in the Tg
7 Figure 7 – DSC curves
of CR group formulati-
ons with higher HaO
loading
of the formulations prepared with 15 phr
of EHaO occured. The Tg’s of formulations
of NBR group are shown in Table 8. DSC
curves of NBR formulations are shown in
Fig 10 and 11.
These varied Tg’s can be explained by
the polarity of subject rubbers and oils.
The less the polarity difference, the more
the compatibility[26]. The polarity of NBR
(33% ACN) is much higher than that of CR
rubber [27]; and the polarity of EHaO is
higher than that of HaO [28]. The polarity
of CR is closer to HaO and EHaO. Therefo-
re, the highest plastization effect was ob-
served in CR formulations containing HaO
and the lowest effect was observed in
NBR formulations containing HaO as a
result of the order of compatibility which
is shown as CR+EHaO > CR+HaO >
NBR+EHaO > NBR+HaO.

Oil resistance performance

Oil swelling performance of CR and NBR
group formulations are shown in Table 7
and Table 8 respectively. It was observed
that formulations prepared with both
HaO and EHaO had very high oil swelling;
and that the formulations containing
HaO had lower swelling compared to the
ones prepared with EHaO. As for NBR
group, oil swelling of these formulations
7 Tg and oil resistance performance of formulations of CR group increased with increased oil loading un-
Oil phr Onset (°C) Midpoint-Tg (°C) Volume change in oil % like CR group. Oil swelling of NBR group
formulations were much lower than that
HaO
of CR group as expected.
0 -37,60 -36,16 69,09
Oil swelling performance of oils can be
10 -42,55 -42,94 60,60 explained by polarity of subject oils and
20 -44,87 -43,43 51,95 rubbers. In accordance with the rule of like
30 -50,61 -50,24 50,13 dissolve like, HaO and EHaO are extracted
40 -62,32 -62,46 46,21 to a high extent by IRM 903 oil due to their
50 -64,91 -64,61 45,64 polarity being very close to that of IRM
EHaO 903 oil and CR rubber. Therefore, high vo-
10 -47,39 -47,60 90,01 lume change and swelling in the rubber
were observed. Lower volume change of
20 -50,90 -50,46 65,28
NBR rubber compounds can be explained
30 -52,79 -49,02 63,63
by higher polarity differences between the
40 -60,07 -59,52 60,52 NBR rubber and the oils (HaO and EHaO)
50 -66,31 -60,63 60,33 compared to CR rubber[29].

8 Tg and oil resistance performance of formulations of NBR group Conclusion

Oil phr Onset (°C) Midpoint-Tg (°C) Volume change in oil % As the concerns on synthetic or mineral
based lubricants increase due to their un-
HaO
favorable impact on the environment and
0 -22,00 -23,37 9,78 human health, there has been a steady in-
5 -22,78 -21,33 13,91 crease in the demand of vegetable oil
10 -23,86 -25,07 13,24 based lubricants. In this study, hazelnut oil
15 -24,16 -24,66 17,20 (HaO) and its epoxidized product (EHaO)
EHaO were used as plasticizers in CR and NBR
5 -22,69 -23,42 11,45 rubber compounds. It was found that the
compounds prepared with CR and HaO in-
10 -23,46 -25,12 12,78
dicated a remarkable decrease in Tg and
15 -25,71 -25,74 13,79 -50 °C of Tg of unplasticized rubber com-

www.kgk-rubberpoint.de KGK · 10 2012 53

 ROHSTOFFE UND ANWENDUNGEN
RAW MATERIALS AND APPLICATIONS

pound dropped to -66 °C. The similar but 8 Figure 8 – DSC curves

lesser drop in Tg was achieved with EHaO. of CR group formulati-
The little drop in Tg was found for com- ons with lower EHaO
pounds prepared with NBR and EHaO. Oil loading
swelling performance of CR rubber was
improved remarkably with both HaO and
EHaO with 35 % less volume change.

Acknowledgment
Compounding and tests have been done
in the laborotory of DRC Kauçuk Sanayii
A.Ş., DSC tests have been done at Chemi-
cal Engineering Department, Kocaeli
University. Ordu Soya Sanayii supplied
the oil. The authors would like to thank 9 Figure 9 – DSC curves
to Dr. Bağdagül Karaağaç, Dr. Mustafa of CR group formulati-
Yasin Şen, Hümeyra Bozkurt and DRC and ons with higher EHaO
Ordu Soya Sanayii for the support. loading

References
[1 ] George Wypych, Handbook of Plasticizers,
(2004) ChemTech Publishing, 3.
[2] E ugene R. Bertozzi, Robert F. Hoffman, Robert
Barcley, United State Patent: 4,061, (1977), 612.
[3] Clara D. Craver, Charles E. Carraher, Appl. Po-
lym. Sci., (2000) 167.
[4] Charles E. Wilkes, James W. Summers, PVC
Handbook, Amazon.co.uk, (2005) 178.
[5] T.D. Stark, H.Choi, P.W.Diebel, GFR Magazine, Figure 10 – DSC curves
10
23,2 (2005) 4. of NBR group formula-
[6] Charles A. Staples, Phthalate esters, Springer, tions with different
(2003), XIV, 5. HaO loading
[7] http://www.fda.gov/cher/minutes/
plast1010899.html
[8] J. Raloff, Girls May Face Risks from Phthala-
tes, Science News , 158 (2000) 165 .
[9] European Chemical Agency website, Candidate List of
Substances of Very High Concern for Authorization.
[10] K. Karadeniz, KGK, 2011
[11] I.S. Rhee, NLG Spokesman 60 (1996) 28.
[12] S.J. Randles, M. J. Synth. Lubr, 9, (1992) 145.
[13] S. Asadauskas, M.J. Perez, Lubr. Eng, 52 (12)
(1996), 877.
[14] K. Aramaki, H.M. Khalid, J. Oleo Sci, 53 (11) Figure 11 – DSC curves
11
(2004), 557. of NBR group formula-
[15] S.Z. Erhan, A. Adhvaryu, Z.Liu, U.S. Patent tions with different
6,583,(2003) 302. EHaO loading
[16] H.S. Hwang, S.Z. Erhan, J.Am. Oil Chem.Soc.,
78 (12), (2001), 1179.
[17] S.K. Moore, Chem.Week, No. 45, (1999) 17.
[18] U.S. Patent, 3,970, (1976) 628.
[19] Soo-Jin Park, Fan-Long Jin, Jae-Rock Lee, Ma-
cromol. Rapid Commun. 25, (2004) 724.
[20] Brajendra K. Sharma, Zengshe Liu, J. Agric.
Food Chem., 56, (2008) 3049.
[21] S.V. Patel, M. Gilbert, Plast. Rub. Process.Ap-
pl. 5(1) (1985) 85.
[22] T.R. Kukreja, R.C. Chauhan, S. Choe, J. Appl. Chem. Soc.,76, (1999), 1211. Vanderbilt, Norwalk, CT.
Polym. , 87, (2003) 1574. [25] Rickey J. Seyler, ASTM International, p 235 [28] H. Lizhi, K. Toyoda, I. Ihara, J. Food Eng. 88,
[23] L. Yang, H.Dai, A. Yi, B.Lin and G.Li, J. Therm. [26] C.D. Craver, C.E. Carraher, Applied Polymer (2008) 151.
Anal. Calorim., 93, (2008), 875. Science: 21 st century, (2000), 167. [29] M.J. Forrest, Rubber Analysis: Polymers,
[24] Chaohua Wang, Sevim Erhan, J. Am. Oil [27] R.O. Babbit, Rubber Handbook, (1978) R.T. Compounds, Products, (2001), 54 .

54 KGK · 10 2012 www.kgk-rubberpoint.de