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 Materials Chemistry and Physics 190 (2017) 25e30

Contents lists available at ScienceDirect

Materials Chemistry and Physics

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

PVC materials without migration obtained by chemical modification of

azide-functionalized PVC and triethyl citrate plasticizer
Puyou Jia a, Lihong Hu a, b, Guodong Feng a, Caiying Bo a, Meng Zhang a, b, **,
Yonghong Zhou a, *
a
Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry (CAF), National Engineering Lab for Biomass Chemical Utilization, Key Lab
on Forest Chemical Engineering, State Forestry Administration, Key Lab of Biomass Energy and Materials, Jiangsu Province, 16 Suojin North Road, Nanjing
210042, PR China
b
Institute of New Technology of Forestry, Chinese Academy of Forest (CAF), Beijing 100091, PR China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

PVC materials were modified with

bio-based triethyl citrate.

Modified PVC materials exhibited
near-zero migration in four different
solvent.

Modified PVC materials have poten-
tial application in durable plastic
products.

a r t i c l e i n f o a b s t r a c t

Article history: In the study, PVC material modified with bio-based triethyl citrate plasticizer was synthesized. PVC was
Received 19 October 2016 first reacted with sodium azide in order to get the azide-functionalized PVC (PVC-N3). Then the modified
Received in revised form PVC material (M-PVC) was prepared by the reaction of PVC-N3 and propargyl ether triethyl citrate. The
28 December 2016
PVC material was characterized with FT-IR, H1 NMR, elemental analysis, GPC, TGA and DSC. The obtained
Accepted 29 December 2016
Available online 2 January 2017
M-PVC material has higher thermal stability and lower glass-transition temperature compared to plas-
ticized PVC with dioctyl phthalate (DOP). It exhibited near-zero migration in four different solvents
(distilled water, 10% (v/v) ethanol, 30% (w/v) acetic acid and petroleum ether). The method provides
Keywords:
Poly(vinyl chloride)
general method for efficient use of biomass resources based plasticizer.
Plasticizer © 2017 Elsevier B.V. All rights reserved.
Triethyl citrate
Migration

1. Introduction
* Corresponding author.
** Corresponding author. Institute of Chemical Industry of Forest Products, Chi-
nese Academy of Forestry (CAF), National Engineering Lab for Biomass Chemical PVC is the third most widely produced polymer in the word,
Utilization, Key Lab on Forest Chemical Engineering, State Forestry Administration, with its excellent mechanical strength, thermal stability, flame
Key Lab of Biomass Energy and Materials, Jiangsu Province, 16 Suojin North Road, retardancy and insulation characteristics, has been widely used as a
Nanjing 210042, PR China.
high performance resin in many products such as in food
E-mail address: yhzhou777@sina.com (Y. Zhou).

http://dx.doi.org/10.1016/j.matchemphys.2016.12.072
0254-0584/© 2017 Elsevier B.V. All rights reserved.
26 P. Jia et al. / Materials Chemistry and Physics 190 (2017) 25e30
packaging, pipes, toys, medical devices, wire and cable [1,2]. Un-
fortunately, pure PVC is so brittle cannot be processed for extrusion
molding to obtain consumer products. PVC is usually mixed with
amounts of plasticizers, up to 70% by weight [3]. PVC products
account for approximately 80% of all types of plasticizers consumed
in China [4]. Dioctyl phthalate (DOP) and dibutyl phthalate (DBP),
as the main commercial plasticizers easily migrate into surround-
ing and reduce performance of PVC products. The loss of plasticizer
cannot maintained the properties of the PVC products long stable,
as well as potential toxicity to human body [5e12]. Many alterna-
tives to phthalate plasticizers have been explored. Hundreds of
non-toxic plasticizer derived from renewable resources have been
developed or used as commercial plasticizer such as cardanol-
based plasticizer [13], epoxidized sunflower oil [14], epoxidized
safflower oil [15], glycerol esters [16], rice fatty acid [1], triethyl
citrate [17], ctric acid [18] and acetyl tri-n-butyl citrate [19]. How-
ever, all of these plasticizers is external plasticizer; migration can
not be avoided with the increasing of time. The use of internal
plasticizers can avoid migration of plasticizer from PVC matrix,
because internal plasticizers are the parts of the polymer matrix
[20]. Internal plasticizers can be prepared via chemical modifica-
tion of polymer matrix. Recently, Ddina et al. synthesized the full-
erenated PVC by the chemical reaction of azido-functional PVC with
C60. [21] The obtained PVC materials retained the electronic prop-
erties of C60, and the processability of PVC was maintained [22].
Lafarge et al. developped new bacteria repellent PVC materials by
chemical synthesis with bioactive polysaccharides and PVC mate-
rials [23]. Kiskan et al. studied novel side-chain benzoxazine
functional polyvinylchloride (PVC-Benzoxazine) [24]. The obtained
PVC materials presented more thermal stable than that of pure PVC.
In addition, macromolecular photoinitiators [25], antimicrobial
aliphatic copolyester [26], one component polymeric photoinitiator
[27], polymeric architectures [28], degradable model networks and
functional telechelics [29,30] were also prepared with chemical
modification of PVC.
In the present work, the modified PVC (M-PVC) material was
prepared by the addition of propargyl ether bio-based triethyl cit-
rate onto azide-functionalized PVC (PVC-N3). The final product was
expected to retain the near-zero migration. The chemical structure,
molecular mass and thermal properties were investigated. Also, the
degree of migration of M-PVC in four different solvents (distilled
water, 10% (v/v) ethanol, 30% (w/v) acetic acid and petroleum ether)
was examined. The method provides general method for efficient
use of biomass resources based plasticizer.
2. Experimental section
2.1. Materials
Triethyl citrate, propargyl bromide solution, potassium car-
bonate, sodium azide, N,N-dimethylformamide(DMF), methanol,
acetone, cuprous bromide, 5,5-dimethyl-2,2-dipyridyl and dioctyl
phthalate (DOP) were kindly provided by Nanjing Chemical Re-
agent Co., Ltd. Polyvinyl chloride (PVC) was supplied by Hanwha
(South Korea).
2.2. Synthesis of propargyl ether triethyl citrate
Propargyl ether triethyl citrate was prepared by dissolving 13.8 g
(50 mmol) of triethyl citrate, 6.54 g (55 mmol) of propargyl bro-
mide solution, 7.6 g (55 mmol) of potassium carbonate in 30 mL of
acetone. The mixture was stirred at 65  C for 12 h. Then the mixture
was washed with deionized water three times. The solution was
purred by evaporating under vacuum. Fig. 1 showed the synthetic
route of propargyl ether triethyl citrate (Yield:97%).
2.3. Synthesis of azide-functionalized PVC (PVC-N3)
PVC-N3 was prepared by dissolving 2.0 g of PVC and 2.0 g of
NaN3 in 100 mL of DMF. The solvent was allowed to stir at 30  C for
24 h and precipitated into water/methanol mixture (1/1 by vol-
ume), and dried in a vacuum to obtain the PVC- N3(Yield:95%). The
synthetic route of PVC- N3 was presented in Fig. 1.
2.4. Preparation of modified PVC (M-PVC)
Modified PVC (M-PVC) was prepared by dissolving 0.64 g of
PVC-N3, 1.02 g (6 mmol) of propargyl ether triethyl citrate, 1 g
(6 mmol) of cuprous bromide, 1.82 g (14 mmol) of 5,5-dimethyl-
2,2-dipyridyl in 20 mL of DMF, which were introduced in a three-
neck flask which was equipped with a mechanical stirrer, nitro-
gen pipe and thermometer. The mixture was stirred at 30  C for
24 h. The product was filtered to remove the copper salts, then the
mixture was precipitated into water/methanol mixture (1/1 by
volume) and dried in a vacuum to obtain the M-PVC(Yield:92%).
The preparation of M-PVC was presented in Fig. 1.
2.5. Preparation of pure PVC blend and PVC-DOP blend (D-PVC)
PVC blend was prepared by dissolving 20 g of PVC and 8 g of
DOP in 100 mL of THF. The mixture was thoroughly agitated using
a mechanical agitator at 160 rpm for 1 h at 60  C until the mixture
presented clear and transparent. The samples were then cast into
Petri dishes (diameter 12 cm) and dried at ambient temperature
for 7 days to remove traces of residual solvent and to obtain thin
films.
2.6. Characterization and measurements
Fourier transform infrared (FT-IR) spectra of PVC, PVC-N3 and
M-PVC were investigated on a Nicolet iS10 FTIR measurement
(Nicolet Instrument Crop., USA). The spectra were acquired in the
range of 4000 cm1 to 500 cm1 at a resolution of 4 cm1.
1
H NMR measurements were conducted on an AV-400 NMR
spectrometer (Bruker Instrument Crop., Germany) at a frequency of
400 MHz CDCl3 was used as solvent and tetrametnylsilane (TMS) as
an internal standard.
Elemental analysis was conducted on an elemental PE-2400
analyzer (PERKINELMER Instrument Crop., USA).
Molecular weight of PVC and M-PVC was measured by using an
Efficient gel chromatograph made by Waters, USA at 30  C (flow
rate: 1 mL/min, column: mixed PL gel 300  718 mm, 25 mm) using
THF as solvent.
Thermogravimetric analysis (TGA) was carried out using a
TG209F1 TGA thermal analysis instruments (Netzsch Instrument
Crop., Germany) in N2 atmosphere (50 mL/min) at a heating rate of
10  C/min. 5 mg of samples were put into platinum pans and
scanned from 40  C to 600  C.
Glass transition temperature (Tg) was characterized using a
NETZSCH DSC 200 PC analyzer, the temperature ranged
from 60  C to 120  C at a heating rate of 20  C/min [13].
Migration stability of plasticizer was tested in according to
ASTMD1239-98. The test temperature was 23 ± 2  C. The relative
humidity was 50 ± 5%. PVC materials were immersed in four
different solvents (distill water, 10% (v/v) ethanol, 30% (w/v) acetic
acid and petroleum ether). PVC materials were settled in 200 mL of
four solvent after weighting. The solvent extracted PVC products
were rinsed with isooctane and then wiped up using vegetable
parchment 24 h later [31e34]. After drying at 30  C for 24 h and
reweighed. The extraction loss was calculated according to Equa-
tion (1). Equation (1): Degree of migration ¼ [(W1-W2)/W1)]  100,
 P. Jia et al. / Materials Chemistry and Physics 190 (2017) 25e30 27

Fig. 1. Preparation of M-PVC.

where W1 ¼ initial weight of test specimen, and W2 ¼ final weight

of test PVC specimen [35].
Tensile modulus, tensile strength, and elongation at break of
PVC, D-PVC and M-PVC were determined according GB/T
1040.1e2006 (China) by using an E43.104 Universal Testing Ma-
chine (MTS Instrument Crop., China).

3. Results and discussion

3.1. Structure and characterization of M-PVC

The chemical structure of PVC, PVC-N3 and M-PVC was

confirmed by FT-IR. Fig. 2 showed the FT-IR spectra. Compared to
the FT-IR spectrum of PVC, the characteristic absorption peak of -N3
band at 2108 cm1 was obviously presented in FT-IR spectrum of
PVC-N3 [23e25], the characteristic absorption peak of C-Cl band at
680 cm1 presented weaker than that of PVC. The results indicated Fig. 2. FT-IR spectra of PVC, PVC-N3 and M-PVC.
that chlorine groups were converted to azide groups with the use of
sodium azide. The -N3 of PVC-N3 band at 2108 cm1 almost dis-
appeared after the click reaction, the strong absorption peak of Fig. 3 presented the 1H NMR spectra of PVC, PVC-N3 and M-PVC.
ester bonds appeared at 1728 cm1, and the C¼N band appeared at From the 1H NMR spectra of PVC and PVC-N3, the N3-CH-(CH2)- and
the 1550 cm1 [36,37], a new absorption peak of C-O-C appeared at Cl-CH-(CH2) protons (peak aþb of 1H NMR spectra of PVC and PVC-
1185 and 1025 cm1, which derived from the propargyl ether N3) are observed as multiple peaks at 4.4 ppm [25]. Additionally,
triethyl citrate. In addition, the characteristic absorption peak at N3-CH-(CH2)- and Cl-CH-(CH2) protons (peak cþd of 1H NMR
769 cm1 and 857 cm1 correspond to the C-C band showed spectra of PVC and PVC-N3) were detectable as broad signal be-
stronger than that of PVC-N3. All of these results demonstrated that tween 2.4 and 2.7 ppm, indicating that chlorine groups were con-
the propargyl ether triethyl citrate was anchored into PVC chains. verted to azide groups with the use of sodium azide. As seen from
1
H NMR spectra was used to further study the click reaction. the 1H NMR spectra of M-PVC, CH2-CH3 protons (peak e of 1H NMR
28 P. Jia et al. / Materials Chemistry and Physics 190 (2017) 25e30
Fig. 3. 1H NMR spectra of PVC, PVC-N3 and M-PVC.
spectra of M-PVC) are observed as multiple peaks at 1.0e1.2 ppm,
the H3CeCH2-O- protons (peak e of 1H NMR spectra of M-PVC)
were detectable as single signal at 4.1 ppm. All of the results sug-
gested that the propargyl ether triethyl citrate was reacted with
PVC-N3.
Elemental analysis was used to investigate whether PVC was
functionalized by sodium salt. So chlorine groups were converted
to azide groups with the use of sodium salt. The results of the el-
ements analysis for PVC-N3 were:35.13% C; 8.21% H; 18.47% N and
38.19% Cl. Taking into these data including the FT-IR and 1H NMR
spectra, PVC-N3 was obtained.
The formation of high molecular weight M-PVC was confirmed
by GPC. The GPC spectra of PVC and M-PVC were presented in Fig. 4.
The GPC chromatogram of M-PVC shifted to a higher molecular
weight region compared to PVC, while maintaining a monomodal
and low molecular weight distribution. The molecular weights and
polydispersion of PVC and M-PVC were 19529 g/mol and 1.23, and
Fig. 4. GPC spectra of PVC and M-PVC.
Fig. 5. DSC curves of PVC, D-PVC and M-PVC.
29602 g/mol and 1.112, respectively. The single GPC peak with a
clear shift to a higher molecular weight region indicated that no
homopolymer contamination of coupling reactions.
3.2. Property of M-PVC and D-PVC
The plasticizing efficiency of the internal plasticizer can be
probed by the glass transition temperature (Tg) of PVC, D-PVC and
M-PVC using DSC measurements. The DSC curves of PVC, D-PVC
and M-PVC was showed in Fig. 5. The Tg value was showed in
Table 1. The DSC curves of PVC exhibited an exothermic peak
approximately at 87.6  C, corresponding to the Tg of PVC. For D-
PVC, when the content of DOP is 28 wt%, the measured value of D-
PVC was 11.7  C. Compared to PVC, as can be seen, a slight decrease
of Tg of 35.7 C was observed in M-PVC, was attributed to the
destruction of macromolecular chain regularity. The results indi-
cated that covalently bond triazole analogues of triethyl citrate
plasticizer to PVC chains via “Click chemistry”, increase the distance
between PVC chains and decrease the der Waals’ force which
increased segment mobility, and then decrease the Tg of PVC effi-
ciently [13,38,39].
Thermal stability of PVC can be enhanced in the presence of
plasticizers. The reason is that more ester bonds or benzene groups
with high thermal stability existed in the structure of plasticizers
(DOP and triethyl citrate), which limited the decomposition of
those segments with lower-thermal-stability chain segments,
thereby increasing the thermal stability of PVC blends [39e41]. The
results can be found in the study, Fig. 6 presented the TGA curves of
PVC, D-PVC and M-PVC. TGA values including T5 (5% mass loss
temperature) and T15 (15% mass loss temperature) and T50 (50%
mass loss temperature) were summarized in Table 1. These regions
of T5 and T15 are more representative of extrusion and heat-aging
conditions. From Table 1, T5, T15 and T50 of D-PVC and M-PVC are
higher than that of PVC. T5, T15 and T50 of M-PVC were the highest
among the three samples. The results suggested that the both the
Table 1
TGA and DSC data of PVC, D-PVC and M-PVC.
Samples T5/ C T15/ C T50/ C Tg/ C
PVC 178.6 227.8 266.6 87.6
D-PVC 228.6 245.1 314.2 35.7
M-PVC 230.9 248.6 384.3 11.7
 P. Jia et al. / Materials Chemistry and Physics 190 (2017) 25e30 29

Fig. 6. TGA curves of PVC, D-PVC and M-PVC.

Fig. 7. Degree of migration of plasticizers.

internal plasticizer (triazole analogues of triethyl citrate) and analogues of triethyl citrate) was better than external plasticizer
external plasticizer (DOP) used in the study improved the thermal (DOP) to enhance the thermal stability of PVC materials. As the low
stability of PVC materials, the internal plasticizer (triazole molecular weight compounds, DOP volatilize easily from the PVC
30 P. Jia et al. / Materials Chemistry and Physics 190 (2017) 25e30
Table 2
Tensile properties of PVC materials.
Sample Modulus of elasticity Elongation at break Tensile strength
(Mpa) (%) (MPa)
PVC 197.1 167.2 26.6
D-PVC 98.9 408.4 13.1
M-PVC 127.8 360.7 16.2
matrix to environment to cause changes in the long-time proper-
ties of the PVC products, as well as potential toxicity to human
body. The volatilization of DOP at high temperature caused the D-
PVC poorer thermal stability than M-PVC.
Fig. 7 showed the degree of migration of internal plasticizer
(triazole analogues of triethyl citrate) and external plasticizer (DOP)
by four kinds of solvents from D-PVC and M-PVC. As can be seen
from Fig. 7, the degree of migration of DOP in distilled water, 30%
(w/v) acetic acid, 10% (v/v) ethanol and petroleum ether was 1.36%,
1.52%, 1.53% and 3.21%, respectively. In contrast, almost not
migration was observed for internal plasticizer (triazole analogues
of triethyl citrate) in these solvents. The results indicated that the
use of internal plasticizer can avoid migration.
Tensile properties of PVC, D-PVC and M-PVC were presented in
Table 2. As seen from Table 2, tensile strength and elongation at
break of PVC was 26.6 MPa and 167.2%, respectively. Tensile
strength and elongation at break of D-PVC reached 13.1 MPa and
408.4%, respectively. The results indicating DOP played an excellent
plasticizing effect on PVC. However, the loss of DOP cannot be
avoided with the extent of time, which will cause changes of
properties for PVC products and reduce their service life. Tensile
strength and elongation at break of M-PVC was 16.2 MPa and
360.7%, respectively, which indicated that PVC was plasticized via
chemical reaction. The tensile properties and migration tests
illustrated that PVC materials can be plasticized without migration.
M-PVC materials will have practical value in areas with high
durability requirements.
4. Conclusions
Bio-based triethyl citrate was processing and utilization in a
novel method. Plasticized PVC material was successfully modified
with bio-based triethyl citrate for the first time via chemical
modification. One of the consequences of the synthesis plasticized
PVC material is that such modification causes a dramatic change in
PVC chemistry. The obtained modified PVC material exhibited
higher thermal stability and lower glass-transition temperature
compared to plasticized PVC with DOP, and zero migration in four
different solvents (distilled water, 10% (v/v) ethanol, 30% (w/v)
acetic acid and petroleum ether). The method provides general
method for efficient use of biomass resources based plasticizer.
Acknowledgements
This work was supported by the Fundamental Research Funds
from Jiangsu Province Biomass and Materials Laboratory (JSBEM-S-
View publication stats
2017010); Jiangsu Key Lab of Biomass-based Green Fuels and
Chemicals (JSBGFC14002); and the President of the Chinese Acad-
emy of Forestry Foundation (Grant No. CAFYBB2014QB021).
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