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Contents lists available at ScienceDirect

Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

Synthesis of castor oil based plasticizers containing ame retarded

group and their application in poly (vinyl chloride) as secondary
plasticizer
Pu-You Jia a, Cai-Ying Bo a, Li-Qiang Zhang a, Li-Hong Hu a,b, Meng Zhang a,b,*,
Yong-Hong Zhou a,*
a
b

Institute of Chemical Industry of Forest Products, Chinese Academy of Forest (CAF), Nanjing 210042, Jiangsu Province, China
Institute of New Technology of Forestry, Chinese Academy of Forest (CAF), Beijing 100091, China

A R T I C L E I N F O

Article history:
Received 25 July 2014
Received in revised form 7 February 2015
Accepted 10 February 2015
Available online xxx
Keywords:
Castor oil
Epoxidized castor oil
Flame retardant
Plasticizer
Polyvinyl chloride

A B S T R A C T

Epoxidized castor oil (ECO) and castor oil phosphate ester (COPE) were synthesized. Structure of two
functionalized castor oil was characterized with FTIR and 1H NMR. Property of poly (vinyl chloride) PVC
blends plasticized with ECO and (COPE) as secondary plasticizer was studied. The results indicated that
thermal stability of plasticized PVC blends was improved, LOI value of PVC blends cooperated with COPE
could reach 27.8%, ame retardant performance of COPE was put into effect by promoting polymer
carbonization and forming a consolidated and thick ame retardant coating, which is effective to
prohibit the heat ux and air incursion.
2015 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

Introduction
Castor oil (CO) is a versatile vegetable oil, the 90% of its fatty
acid content is 12-hydroxy-90-cis-octadecenoic acid. The rich
chemistry of CO is attributed to its structure (one double C5
5C and
one OH group per fatty acid chain, which makes it a good starting
material for a range of application such as plasticizer, lubricants,
coating, nylon and organic intermediates for some industries
[1]. The most important modication in CO is epoxidation. Like the
other vegetable oil, CO could also be functionalized by epoxidation
with organic peracids or H2O2 [2]. As an important member of
plasticizer products, epoxidized vegetable oil occupies an indispensable position in poly(vinyl chloride) (PVC) industry because of
the advantages of non-toxic, environmental, biodegradable and
renewable raw materials.
Poly(vinyl chloride) (PVC) is the second largest manufactures
resin in the world, its products are widely used in window frames,

* Corresponding authors at: Institute of Chemical Industry of Forest Products,

Chinese Academy of Forest (CAF), Nanjing 210042, Jiangsu Province, China.
Tel.: +86 25 85482520.
E-mail addresses: zhangmeng82@163.com (M. Zhang), yhzhou777@sina.com
(Y.-H. Zhou).

wallpapers, pipes, ooring, cables, bottles, packaging and credit

cards, audio records, medical tubing, blood bags and children toys
[3]. As one of the clearest and toughest plastics, it is difcult to
process because of its high melt viscosity caused by the rigid chain
structure, resulting a relatively high processing temperature and
high screw torque [4]. The main resolution of the problem is to add
inert plasticizers, tend to impair the mechanical and thermal
properties of the nal product [5]. Plasticizer plays an important
role in improving the exibility and process ability of PVC by
lowing the second order transition temperature, the transition
temperature (Tg) [6]. The Council of the IUPAC (International Union
of Pure and Applied Chemistry) dened a plasticizer as a
substance or material incorporated in a material to increase its
exibility, workability or distensibility. Phthalates is the main
plasticizer additives of PVC, which have been used around the
world for years because of excellent plasticizing effect, but
phthalates may migrate from PVC products to environments
when the materials contact with biological uids, which will take
potential risks to human health when it is used in food packing,
automotive products, insect repellents, blood storage bags and
medical devices [710]. And the raw materials of phthalate are
petroleum, scarcity of petroleum resources and the rising cost of
petroleum products have led to the increasing trend toward

http://dx.doi.org/10.1016/j.jiec.2015.02.017
1226-086X/ 2015 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.

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developing of alternate sources of materials for industrial uses. In

recent years, the preparation of PVC plasticizer from renewable
sources such as sunower oil [11], safower Oil [12], glycerol [13],
oleic acid [14], rice fatty acid [15], cardanol [16] soybean oil
[17,18], epoxidized sunower oil [19] and glycerol tri-isovalerate
[20] is currently receiving increasing attention because of the
economic and environment concerns. Epoxidized castor oil has
been used as plasticizer of PVC for years, but the synthesis of castor
oil including ame retardant group and the mechanism of ame
retardant has never been reported. In this study, we look forward
to preparing a novel bio-based plasticizer containing retardant
group based castor oil, and partly to replace the phthalate as
plasticizer of PVC.
In this study, ECO was synthesized from CO, glacial acetic acid,
phosphate and hydrogen peroxide (H2O2). Then ECO was the rst
time to convert into ame-retardant COPE by reaction with diethyl
phosphate using triphenyphosphine as catalyst. The FTIR and 1H
NMR were employed to characterize the structure of ECO and
COPE. PVC blends were prepared using ECO and COPE as secondary
plasticizer, respectively. The reaction between PVC and plasticizer
was studied, and the mechanism of degradation and retardant
performance of COPE was discussed.

Fig. 1. Synthesis of ECO and COPE.

Experimental
Materials
Phosphate, anhydrous acetic acid, phosphorus pentoxide,
triethyl phosphate, calcium stearate, zinc stearate and triphenylphosphine were obtained from Nanjing Chemcial Reagent Co., Ltd.
Sodium hydroxide, hydrogen peroxide, methylbenzene were
supplied by Aladdin Chemical Co., Ltd. Castor oil (chemically
pure) was provided by Nanjing Feilong CompositesCo., Ltd. (China).
Polyvinyl chloride (PVC) was supplied by Hanwha (South Korea)
with K value 65.0 and degree of polymerization 1300  100.
Synthesis of epoxy castor oil (ECO)
100 g castor oil (CO), 15 g glacial acetic acid and 1 g phosphate
were mixed in a four-necked round-bottom ask which was
equipped with a mechanical stirrer, condenser pipe, thermometer
and constant pressure funnel. 80 g hydrogen peroxide solution was
dropped in the reaction in 30 min and stirred at 50 8C for 4 h to
nish epoxidation reaction. Then the reaction mixture was
separated from water with separating funnel and washed 3 times
with distilled water, then removed the water with a rotary
evaporator at 60 8C. The chemical reaction process of epoxidized
castor oil (ECO) was shown in Fig. 1.
Synthesis of diethyl phosphate (COPE)
45.5 g triethyl phosphate was placed in a three-necked roundbottom ask equipped with a mechanical stirrer, a thermometer
and a condenser tube, 28.2 g phosphorus pentoxide was mixed in
the three-necked round-bottom ask under 50 8C in 2 h. The
polyphosphate intermediate was obtained. Then 16.8 g ethyl
alcohol absolute was dropped in the polyphosphate intermediate
and stirred at 100110 8C for 16 h to nish the reaction. The mass
fraction of diethyl phosphate in the product was 80.2%.
Synthesis of ame retardant castor oil
100 g epoxidized castor oil (ECO) and 80 g toluene were
mixed in a three-necked round-bottom ask equipped with a
poly tetrauoroethylene stirrer, a thermometer and a condenser
pipe. The mixture of diethyl phosphate (30 g), toluene (80 g) and

triphenyphosphine (0.1 g) were dropped in the reaction in 30 min

at 40 8C. The reaction proceeded with continuous stirring at 75 8C
for 4 h. Then the reaction mixture was cooled to room temperature
and washed to PH = 7 with sodium hydroxide solution and washed
3 times with distilled water, then removed the water with a rotary
evaporator at 60 8C. The chemical reaction process of COPE was
shown in Fig. 1.
Preparation of blends
PVC blends were melting process at 165 8C for 5 min at 50 rpm
using Poly Lab Torque rheometer (Hakke Instrument Crop.,
Germany). PVC resin was pre-treated by drying at 60 8C for 2 h
to eliminate possible absorbed water on the surface of particle.
Formulations used for preparing plasticized PVC blends were
showed in Table 1. Dumbbell-shaped samples of blends were
molded on a MiniJetII Micro-injection molding machine (Hakke
Instrument Crop. Germany) according GB/T 17037.1-1997(China).
Mounding conditions were set at 165 8C for 5 min at 550 bar.
Measurements
The FTIR studies were carried out using a Nicolet iS10 FT-IR
(Nicolet Instrument Crop., USA). The spectra were acquired in the
range of 4000 to 650 cm1 at a resolution of 4 cm1.
Proton nuclear magnetic resonance (1H NMR) spectra for the
plasticizers based on castor oil were recorded in CDCl3 on an AV300 instrument with tetrametnylsilane as an internal standard.
PVC blends were melt process at 165 8C for 5 min at 50 rpm
using Poly Lab Torque rheometer (Hakke Insturment Crop.,
Germany). Formulations used for preparing plasticized PVC blends
were shown in Table 1.
TGA and DTG were carried out in a TG209F1 TGA thermal
analysis instruments (Netzsch Instrument Crop., German) in N2
atmosphere (50 ml/min) at a heating rate of 10 8C/min. The
samples were put into platinum pans and scanned from ambient
temperature to 600 8C.
The combustion test was carried according to the standard
of Plastics-Determination of burning behavior by oxygen index
(GB/T 2406.1-2008. China) using JF-3 Oxygen index measuring
instrument (Nanjing Lei Instrument Co. Ltd., China). Size
(4  10  80 mm3) of samples was prepared.

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Table 1
Composition of PVC blend plasticized with ECO and COPE.
Samples
a
b
c
d
e

PVC (g)

DOP (g)

ECO (g)

COPE (g)

Calcium stearate (g)

Zinc stearate (g)

100
100
100
100
100

40
35
30
35
30

0
5
10
0
0

0
0
0
5
10

1
1
1
1
1

1
1
1
1
1

A Hitachi 3400-1 (Hitachi, Japan) scanning electron microscope

instrument, operated at 12 kV, was used to observe the surface of
PVC blend and residual char of PVC blends. The fracture of all
surfaces was sputtered with gold.
The dynamic mechanical property was examined via a DMTA
Q800 (TA Instruments, US). The oscillatory frequency of the
dynamic test was 1 Hz. The temperature was raised at a rate of
3 8C/min in the range of 80100 8C.
The crystallinity data were obtained via X-ray diffraction
(XRD) with a D8 FOCUS (BRUKER, Germany) operated at 45 kV
and 40 mA using Cu-Ka radiation with a graphite diffracted
beam monochromatic. Data were acquired in a 2theta scale from
108 to 808.
Tensile modulus, tensile strength, and elongation at break
were determined according GB/T 1040.1-2006 (China) under
ambient conditions, using E43.104 Universal Testing Machine
(MTS Instrument Crop., China). The reported values were the
average of at least. Hardness was determined using a HT-6510D
Shore durometer (Shanghai Jielun, China) according GB/T 3398.22008 (China).
Results and discussion
Infrared spectroscopy (FTIR)
All the steps of the synthesis of ECO and COPE were followed by
FTIR spectroscopy, GPC chromatography and 1H NMR spectroscopy. FTIR spectra of CO, ECO and COPE were compared in Fig. 2. In
Fig. 2, two characteristic peaks around 3007.7 cm1 and
1655.81 cm1, associated with 5
5CH and C5
5C vibration, were
observed in the spectra of CO. Compared to the spectroscopy of
ECO, both of the characteristic peaks disappeared, and the
characteristic peak of COC vibration was observed around

968 cm1 and 1057 cm1. These data may indicate that the C5
5C
double bond was fully expended in the formation of the epoxy
groups.
Fig. 2 also showed the FTIR spectra and the parameters of COPE.
The peak at 1029.61 cm1 was assigned to POC symmetric
bending vibration, and POCH2CH3 was observed. The epoxy
group (at 968 cm1 and 1057 cm1) of ECO disappeared in the FTIR
spectrum of COPE while the absorbance of POC groups at
1029.61 cm1 had appeared, indicating that a reaction of POH of
diethyl phosphate with COPE had nished.
1

H NMR spectra

The 1H NMR spectrum of CO, ECO and COPE are depicted in

Figs. 35. Fig. 3 illustrates the 1H NMR spectrum of CO, the
methyl protons were at d = 0.9 ppm (peak 1), the fatty acid
protons [(CH2)CO] (peak 6) were at d = 2.4 ppm, and the
methylene protons of glycerol were in the range of d = 4.1
4.4 ppm (peak 9). These peaks are always taken as reference,
because the intensity of the peaks should not be altered
throughout the epoxidation and ring-opening addition reaction
[21]. The methylene protons of glycerol was at d = 4.15 ppm
(peak 8), methylene protons attached to hydroxyl (CHOH)
were in the range of d = 3.6 ppm (peak 7), the peak at d = 5.3 ppm
(peak 10) is corresponding to the double bond protons CH5
5CH
of fatty acid, while the peak d = 2.1 ppm (peak 5) was assigned to
CH2 of HOCCH2C5
5C and the range of d = 1.4 ppm (peak 2)
was assigned to the other CH2.
Fig. 4 showed the 1H NMR spectrum of ECO, as the epoxidation
reaction processed, the bands at d = 5.35.6 ppm (peak 10) of the
spectrum of CO associated with the CH5
5CH were converted to
two resonances at 2.93.2 ppm (peak 10) corresponding to protons
on the epoxy groups of ECO (Fig. 4), it indicated that the CH5
5CH
bonds of CO was reacted with H2O2. In addition, the peak at
d = 5.3 ppm (peak 10) is corresponding to the double bond protons
CH5
5CH of fatty acid, because the epoxidation reaction was not
completed.
Fig. 5 presented the 1H NMR spectrum of COPE. The protons of
POCH were at d = 1.7 ppm (peak 4). The protons signals in the
5.35.6 ppm (peak 10, Fig. 4) associated with COC bonds were
replaced in the spectrum of COPE by a peak at d = 1.7 ppm (peak 4,
Fig. 5), which is corresponded to protons of POCH
[22,23]. Compared to the 1H NMR of CO, ECO and COPE, we can
conclude that the ECO and COPE were prepared.
Blend mixtures and torque evaluation

Fig. 2. FTIR spectra of CO, ECO and COPE.

The melting behavior of PVC blend was veried by collecting

the processing data during mixing in the Haake chamber. The three
important variables in this process are rotating speed, rotor torque
and chamber temperature. The chamber temperature and rotating
speed was xed, and the torque data were collected and related
directly to the melt viscosity, the material resistance to ow.
The melt temperature remained approximately constant during
processing. The torque rheological curves of PVC blends and the
gure of torque values relative to the proportion of plasticizer in

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Fig. 3. 1H NMR spectra of CO.

Fig. 4. 1H NMR spectra of ECO.

Fig. 5. 1H NMR spectra of COPE.

blends were shown in Figs. 6 and 7. It was seen from Fig. 6, the
point A is corresponding to feeding peak which indicates
maximum torque, the point B, C, D and E is corresponding to
stable torque, minimum torque, starting point of degradation and
end of degradation, respectively. PVC material should be taken
from torque rheometer and the thermoplastic processing should
be stopped at the point of stable torque. PVC will be started

degrading after the time. Fig. 7 presents the torque values relative
to the proportion of plasticizer in PVC blends for the processing
time of 5 min.
From Fig. 7, with the increasing of ECO and COPE, the torque of
PVC blends increased from 11.6 N m (a) to 16 N m (c) and 16.5 N m
(d), which corresponds to 37.93% and 42.24% increment, respectively. The torque increment could increase the melt viscosity and

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Fig. 8. TGA and DTA curves of PVC blends.

Fig. 6. The torque rheological curve of PVC blend.

and decomposition of water, DOP, HCl and small molecules. The

second stage at around 250440 8C is the fastest and could be
attributed to the formation and stoichiometric elimination of HCl.
The last stage at above 440 8C is attributed to cross linking
containing C5
5C bonds. Thermal degradation of polyenes involves
cyclization and splitting of chains [5,6,15]. DTG curves of PVC
blends showed two degradation peaks at around 290 8C and
460 8C, and PVC blends plasticized with ECO and COPE showed
similar behavior with two mass loss peaks. Both mass peaks are
corresponding to two faster thermal degradation stages.
The thermal properties data of these PVC blends were
summarized in Table 2, including decomposition temperature
(Td), 10% and 50% weight-loss temperature (T10 and T50) and
temperature at the maximum weight-loss temperature rate (TP).
As the increase of content of ECO and COPE, T10, Td and TP increased.
The samples of d and e increased obvious. Because the diethyl
phosphate had degraded and phosphinic acid was generated with
the temperature increasing. Phosphinic acid make PVC dechlorination to produce carbonization zone and O2 and heat were
prevented, which make PVC blends thermal stability.
Fig. 7. Torque variation in relation to the plasticizer content.

would be not conductive to thermoplastic processing of PVC

blends.
Thermo gravimetric analysis (TGA) and Differential thermal
gravity (DTG)
TGA and DTG were used to study the thermal degradation of
PVC plasticized with ECO and COPE. The parameters and curves of
TGA and DTG were presented in Table 2 and Fig. 8, respectively. It
was seen from Fig. 8; all of the PVC blends were thermally stable in
N2 atmosphere below 90 8C and divided into a three-stage thermal
degradation process above the temperature. The rst stage
degradation at around 90250 8C is corresponding to evaporation

Flame retardant performance analysis

The easy extinction of PVC blends has been evaluated by the LOI
test according to the standard of Plastics-Determination of burning
behavior by oxygen index (GB/T 2406.1-2008. China) using JF-3
Oxygen index measuring instrument (Nanjing Lei Instrument Co.
Ltd., China). Size (4  10  80 mm3) of samples was prepared. To
assessed ame retardant properties of these samples, LOI tests
were conducted and the LOI variation in relation to plasticizer
content was depicted in Fig. 9. From Fig. 9, the LOI value decreased
from 24.1% (a) to 23.3% (c) with the addition of 10 g ECO, and the
LOI value increased from 24.1% (a) to 27.8% (e) with the addition of
10 g COPE. Generally, materials exhibited (LOI) values greater than
26% will show self-extinguishing behaviors and considered to be
good amer retardant [24,25]. Therefore, ECO could not be used as
ame retardant of PVC, while the increase of LOI value indicated

Table 2
The parameters of TGA and DTG of PVC blends.
Samples
a
b
c
d
e

Td (8C)

T10 (8C)

T50 (8C)

TP1 (8C)

TP2 (8C)

Tg (8C)

Residual (%)

249.4
254.9
262.7
276
278.7

258.1
255.3
263.1
266.2
270

283.2
304.9
310
306.3
324.6

278.9
291.7
302.5
300.02
314.8

457.3
469.8
466
467.7
470.4

35.3
42.6
44.3
46.0
48.5

17.02
12.81
10.71
10.15
5.91

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Fig. 9. LOI variation in relation to plasticizer content.

that incorporation of PVC and COPE system has obvious improvement the ame retardant properties of PVC blends.
Fig. 10 showed the SEM images of the residual char after Limit
oxygen index test, Fig. 10(a2), (c2) and (e2) is corresponding to
sample a, c and e, respectively. Surface morphology of residual char
is different comparing to each other with the increase of ECO and
COPE. The char surface of Fig. 10(a2) and (c2) is separated by a net
of cracks. The width of cracks is about 200 mm, and a large number
of irregular micro hubble structures distributed on the surface of
char residue. The incomplete char coat cannot effectively prohibit
heat ux and air incursion penetrating the underlying heat
polymer. The physical structure of the charring layer plays an
important role in the performance of the ame retardant
[27]. Therefore, ECO could not play any role in the performance
of the ame retardant. On the contrary, the char surface of sample e
is continuous and compact was showed in Fig. 10(e2), and any
crack could not be observed, indicating that the adhesive between
the COPE and the PVC matrix was strong. PO and PC bonds
existed in the structure of COPE make it still thermal stability
under 350 8C. The existence of diethyl phosphate grafting in the
castor oil phosphate molecular chain, diethyl phosphate degraded
and phosphinic acid was generated when it was burned.

Fig. 10. SEM micrographs of surfaces of PVC blend (a1), SEM micrographs of surfaces of PVC blend (c1), SEM micrographs of surfaces of PVC blend (e1), SEM micrographs of
surfaces of residue (a2), SEM micrographs of surfaces of residue (c2), SEM micrographs of surfaces of residue (e2).

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Metaphosphate and poly metaphosphate would be generated after

dehydration of phosphinic acid. They could promote polymer
carbonization and form a consolidated and thick ame retardant
coating quickly. From Fig. 10(e2), it can be seen that char layer of
the ame retardant coating is consolidated and thick, which is
effectively prohibit the degradation products penetrating the
underlying heated polymer. The ame retardant coating plays an
important role in the performance of the ame retardant.
Comparing with DOP, ECO, sunower oil [11], safower oil [12],
glycerol [13], oleic acid [14], rice fatty acid [15], cardanol [16]
soybean oil [17,18], epoxidized sunower oil [19], glycerol triisovalerate [20], because all the above plasticizers burn easily
which could not play any role on ame retardancy for PVC blends,
but COPE not only plasticizes PVC effectively but also reduces the
ammability of PVC blends.
Scanning electron microscopy (SEM)
The properties of particle lled composites strongly depend on
the dispersion and compatibility of llers in polymer matrix
[24,26]. The SEM images of the surface of PVC plasticized with ECO
and COPE were shown in Fig. 10. Fig. 10(a1), (c1) and (e1) is
corresponding to sample a, c and e, respectively. From Fig. 10(a1), a
large number particle and fractures could be observed on the
external surface of a, the particle appearing on the surface are
properly the result of some plasticizer excess that is scattered
outside the PVC matrix. It caused the eventual migration of
plasticizer out of PVC during processing and using. While PVC
plasticized with ECO and COPE showed homogeneous and smooth
surface as observed in Fig. 10(c1) and (e1). ECO and COPE disperse
in the PVC matrix uniformly and surrounded intimately with PVC
continuous phase, and there is not a clear boundary between them
to be observed. So there are good interfacial adhesion and
plasticization between ECO, COPE plasticizers and PVC.

the content of ECO increased from 0 g to 10 g in PVC blend, and the

Tg increased from 27.5 8C to 49.8 8C with the content of COPE
increased from 0 g to 10 g in PVC blend. This might be due to the
applied force between epoxy bonds or phosphate bonds and
molecular chain of PVC become strong, and decreased the motion
of the molecular chain of PVC.
X-ray diffraction (XRD)
The XRD analysis is employed to determine the structure,
complexation and crystallization of the polymer matrix [28
30]. The XRD diffractograms of PVC blends were depicted in
Fig. 12. From the corresponding angle of the characteristic peaks
and the applying Braggs Law (nl = 2dsinu), for l of 1.542 A, the
interlamellar basal distances (d) could be calculated. The
diffractograms showed two characteristic peaks at 2theta  18.28
18.28 and 24.68, which correspond to interlamellar basal distances
of 0.49 A and 3.62 A, respectively. According the XRD diffractograms, no difference in the crystalline of the PVC blends and the
PVC blends plasticized with ECO and COPE. It indicated that the
both ECO and COPE did not change the crystallinity of PVC blends.
The results indicated that the effect of ECO and COPE on
crystallinity of PVC blends is similar to that of DOP and polyester
plasticizer [15], all of the plasticizer could not change the
crystallinity of PVC blends.
Tensile properties

The glass transition temperature (Tg) of the PVC blends was

characterized by DMA; the DMA curves were shown in Fig. 11. Only
a tan d peak existed in every DMA curve could be observed, which
indicated that compatibility of the PVC and two kinds of functional
plasticizers were excellent. The DMA data indicated that the tan d
peak shift to higher temperature with increasing content of ECO
and COPE. From Table 2, the Tg increased from 27.5 8C to 43 8C with

Mechanical properties of PVC blends were characterized by using

E43.104 Universal Testing Machine (MTS Instrument Crop., China)
according GB/T 1040.1-2006 (China) under ambient conditions.
Table 3 summarized the values of the mechanical properties of PVC
blends. From Table 3, the inuence of the addition of different
content ECO and COPE for PVC blends could be observed. With the
addition of ECO and COPE in the PVC blends, it caused increment in
tensile strength, hardness and reduction in elongation at break. It is
accordance with the common rule that the plasticizer can increase
the elongation at break. The results could illustrate that the
plasticizing efciency of ECO and COPE in PVC is similar to DOP.
The reason may be that ECO and COPE molecular have similar
atmosphere to DOP molecular, and the interaction between
plasticizer molecular and PVC molecular is similar to the interaction
between DOP molecular and PVC molecular. So ECO and COPE could
take place of DOP partly as an effective plasticizer for PVC.

Fig. 11. DMA curves of PVC blends.

Fig. 12. X-ray diffractograms from PVC blends.

Dynamic mechanical analysis (DMA)

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8
Table 3
The tensile properties of PVC blends.
Samples
a
b
c
d
e

Tensile strength (MPa)

Elongation at break (%)

Modulus of elasticity (MPa)

Hardness (Shore D)

16.32
16.60
16.77
16.46
16.68

350.12
293.91
243.24
220.79
194.19

6.8
28.29
12.39
36.75
67.5

38
39
46
43
45

Conclusions
Petroleum-based plasticizer materials cannot be replaced
completely by pure bio source materials because of poor
performance competition. Then to develop partially substituted
petroleum plasticizer materials becomes more realistic. In this
study, two kinds of PVC plasticizers based on castor oil were
synthesized, and PVC blend system was prepared using ECO
and COPE as auxiliary plasticizer, respectively. As DOP was
replaced by ECO and COPE gradually, the torque evaluation
and SEM showed that both plasticizer increased the melt
viscosity in melting process and improve the compatibility,
which indicated that there is a good interfacial adhesion and
plasticization between ECO, COPE plasticizers and PVC. Thermal
analysis showed that the Td increased from 249.4 8C to 254.9 8C
and 278.7 8C with the content of ECO and COPE was up to 10 g
in PVC blends, and the Tg increased from 35.3 8C to 44.3 8C
and 48.5 8C, respectively. Then XRD analysis indicated that did
not change the crystallinity of PVC blends, and the tensile
properties showed that the plasticizing efciency of ECO and
COPE in PVC is similar to DOP. COPE as a novel biobased
plasticizer containing retardant group, the LOI tests indicated
that the LOI value of PVC blends could increased from 24.2% to
27.8%, the ame retardant performance of COPE was put into
effect by promoting polymer carbonization and forming a
consolidated and thick ame retardant coating quickly, which
is effective to prohibit the heat ux and air incursion. This work
suggests a new research area for synthesis and application of
vegetable oil to produce a functionalized plasticizer, which will
expand the application range of PVC plasticized with COPE
materials.
Acknowledgements
This work was supported by Jiangsu Province Natural Science
Foundation of China (Grant no. BK20141074); the President of

the Chinese Academy of Forestry Foundation (Grant no.

CAFINT2013K01).
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Please cite this article in press as: P.-Y. Jia, et al., J. Ind. Eng. Chem. (2015), http://dx.doi.org/10.1016/j.jiec.2015.02.017