Liquid polyoctahedral silsesquioxanes as an effective and facile

reinforcement for liquid silicone rubber

Jiaotong Sun,1 Junhua Kong,2 Chaobin He 1,2
1
Department of Materials Science & Engineering, National University of Singapore, 9 Engineering Drive 1, 117575 Singapore
2
Agency for Science, Technology and Research (A*STAR), Institute of Materials Research and Engineering, 2 Fusionopolis Way,
138634 Singapore
Correspondence to: C. He ((E-mail: msehc@nus.edu.sg) or (E-mail: cb-he@imre.a-star.edu.sg)).

ABSTRACT: Acrylo polyoctahedral silsesquioxanes (POSS), a liquid POSS derivative with reactive C=C double bond, is used to modify
addition-cured liquid silicone rubber (LSR) as an effective nanofiller for the first time. Significant enhancements on mechanical proper-
ties are obtained. With addition of only 1.5 parts per hundred rubbers (phr) of acrylo POSS to fumed silica-strengthened silicones, the
Young’s modulus and ultimate tensile strength are increased by 432% and 66%, respectively, and the hardness of resulting LSR compos-
ites is improved as well. Proton nuclear magnetic resonance and Fourier transform infrared spectroscopies prove the efficient hydrosily-
lation between Acrylo POSS and hydrosiloxane directly. The thermal stability and morphology investigations also confirm that POSS is
covalently incorporated into the network of silicone rubber. The increment of crosslink density is proved by extraction and swelling
experiment and dynamic mechanical analysis. It can be envisioned that this simple and effective method could help produce high
performance silicone rubber composites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46996.

KEYWORDS: mechanical properties; morphologies; polyhedral oligomeric silsesquioxane; silicone rubber

Received 1 December 2017; accepted 11 July 2018

DOI: 10.1002/app.46996

INTRODUCTION of Si-OH functional groups, the organic R groups in POSS can be

As an inorganic synthetic elastomer, silicone rubber is widely
applied in wide ranges of applications such as adhesives, sealants,
lubricants, and medical devices owing to its good chemical and
thermal stability, excellent weather resistance, and low toxicity.
However, raw silicones normally has extremely poor mechanical
properties and is crumbled easily even under fingernail pressure
because of its intrinsic low cohesive energy resulted from the
weak van der Waals forces between the flexible Si-O-Si backbone.
The most effective way to enhance the mechanical property of
silicone rubbers is to incorporate reinforcing filler such as fumed
silica.1–3 Ansarifar and colleague reported that the tensile
strength of silicone rubber could increase by 100% and 1300%
with incorporation of 10 phr and 60 phr of fumed silica, respec-
tively.2 Such significant improvement was attributed to the strong
hydrogen bonds between silanol functional groups on silica sur-
face and Si-O-Si linkages in silicone rubber (PDMS), and silica’s
high specific surface area. Similarly, Polyoctahedral silsesquiox-
anes (POSS), with a diameter of only 1–2 nm and a chemical
formula (RSiO1.5)8, can be regarded as the smallest silica. Instead
reactive, which makes POSS an excellent building block in cova-
lent nanocomposites. It has been found that POSS-incorporated
polymeric composites possess several attractive properties, such
as increased thermal stability, better fire resistance, and enhance-
ments in modulus.4–9
Recently, several groups used different kinds of vinyl POSS deriv-
atives to vulcanize silanol terminated polydimethylsiloxane
(PDMS) by hydrolytic condensation reaction or to react with
hydride PDMS by addition-type reaction as cross linking
agents.10–22 The enhancement effect of POSS on mechanical
properties, thermal stability and hardness was exhibited in com-
parison with pristine silicone rubber counterpart. However, it is
not persuasive to choose silicone rubbers without fumed silica as
a benchmark since their mechanical properties are usually very
poor. Moreover, the reported works used solid POSS derivatives
as reinforcing agents, and as a result, organic solvents are needed
to facilitate the dispersion of POSS into PDMS. The toxic organic
solvents and complicated procedure inevitably hinder the practi-
cal application of POSS in industry.

Additional Supporting Information may be found in the online version of this article.

© 2018 Wiley Periodicals, Inc.

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In this work, liquid reactive acrylo POSS possessing carbon–carbon
double bond was introduced into LSR as reinforcement. The dis-
persion of liquid reactive acrylo POSS into silicone rubber can be
achieved by compounding using an internal mixer without the aid
of a solvent. Besides, the improvement of mechanical performance
and thermal stability are evident with small incorporation of acrylo
POSS, which is more profound compared with counterpart using
fumed silica as sole strengthening filler. The mechanism behind
such significant enhancement was also elucidated.
EXPERIMENTAL
Materials
The Acrylo POSS cage mixture (MW = 1321.75 g mol−1) with an
inorganic silsesquioxane at the core and eight organic
acryloxypropyl groups attached at the corners of the cage
was purchased from Hybrid Plastics, Inc (Hattiesburg, MS). Vinyl
terminated polydimethylsiloxanes [VPDMS, 1000 centistokes (cSt),
MW = 28 000], Methylhydrosiloxane-dimethylsiloxane copolymer
[HPDMS, 25–35 cSt, MW = 1900–2000, mole % (MeHSiO)= 25–30%]
were supplied by Gelest Inc (Morrisville, PA). Platinum-
divinyltetramethyldisiloxane complex and inhibitor (Andisil
2827-186 L) were purchased from AB Specialty Silicones (Jiangsu,
China). The hydrophilic fumed silica (AEROSIL 380) with a specific
surface area of 380 m2 g−1 was supplied by Evonik Corporation
USA (Parsippany, NJ) and dried at 120
C for 2 h prior to use. Tet-
rahydrofuran (THF) was provided by Sigma-Aldrich (Singapore)
and used as received.
Fabrication of Acrylo POSS-Modified LSR Composites
The synthetic route to acrylo POSS-incorporated LSR composites
is shown in Figure 1. Typically, 50.0 g of VPDMS (3.57 mmol of
O Blending
+ Fumed Silica
Si n Si
Pt catalyzed hydrosilylation
140-200 oC
Fumed Silica
Figure 1. A simple approach to enhanced liquid silicone rubber by Acrylo POSS as a reinforcing nanofiller.
46996 (2 of 8)
C=C) and 30 phr of fumed silica were first blended in a Braben-
der mixer (Germany) for 3 h at ambient temperature and then
for 0.5 h at 170
C. The viscous liquid silicone was obtained after
cooling down to ambient temperature and then mixed with
1.71 g of HPDMS (7.02 mmol of Si-H), 0.25 g of acrylo POSS
(1.51 mmol of C=C), and 1 phr of inhititor in a 100 mL of poly-
tetrafluoroethylene (PTFE) beaker under mechanical stirring for
10 min. 1 phr of Pt catalyst was successively added and stirred
vigorously for another 20 min to ensure homogeneous disper-
sion. The mixture was poured into PTFE molds and then
degassed under vacuum until no bubbles came out. The silicones
in the molds was vulcanized for 2 h at 140
C and then postcured
for another 2 h at 200
C. The obtained LSR sample was denoted
as LSR-1. The other modified LSR and pristine LSR samples were
vulcanized following the same procedure except with different
feedings. The formulations for all LSR samples are given in
Table I. Except for LSR-control, the feeding ratio of Si-H group
to C=C group for other samples remains to be 1.4, which is usu-
ally higher than 1.0 when fumed silica fillers exist in the system.
Extraction and Swelling Experiment
The crosslink densities of LSR composites were estimated by the
extraction and swelling experiment performed in THF. The
2 mm-thick column specimens with diameter of 1.2 cm were cut
from cured sheets and their initial weights were designated as Wi.
The specimens were immersed in 15.00 mL of THF in capped
flasks for 12 h, and then the solvent was exchanged with fresh
THF for another 12 h. The swollen specimens were taken out
from the solvent, and their surfaces were dried with tissue paper.
Before the swollen specimens were dried at 75
C, their weights
(Wsw) were first determined and then the constant weights (Wc)
O O O
Si Si Si Si
n m
H
O O
O O O
O Si
Si
O O
O
O Si OO Si O O
O Si
O O O O Si O
O Si O Si O
O
O O
O O
Acrylo POSS
Acrylo POSS
J. APPL. POLYM. SCI. 2018, DOI: 10.1002/APP.46996
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Table I. The Formulations of Addition-Cured LSR Composites
Samples VPDMS [g] Fumed silica [g]
LSR-0 50.0 15.0
LSR-1 50.0 15.0
LSR-2 50.0 15.0
LSR-3 50.0 15.0
LSR-control 50.0 15.0
of specimens after drying were recorded. The degree of swelling
(Dsw) and the weight percentage of the soluble fraction (Wsol %)
were, respectively, determined by eqs. (1) and (2):
Wsw −Wc
Dsw = × 100% ð1Þ
Wc
Wi − Wc
Wsol % = × 100% ð2Þ
Wi
Characterizations
Thermal stability was studied with thermogravimetric analysis
(TGA) on a TA Instruments Q500 analyzer under nitrogen at a
heating rate of 10
C min−1. Proton nuclear magnetic resonance
(1H NMR) spectroscopy was conducted on a JEOL 500 MHz
spectrometer in d-chloroform. The mixed sample of HPDMS and
Acrylo POSS for 1H NMR test was prepared as follows. HPDMS
(21 mg), Acrylo POSS (3 mg) and Pt catalyst (1 mg) in CDCl3
was added into NMR tube at ambient temperature. The mixture
was homogenized with a shaker for 2 h then subjected to NMR
test. Fourier transform infrared (FTIR) spectroscopy was per-
formed on a Shimadzu IR Tracer-100 spectrometer. Dynamic
mechanical analysis (DMA) was conducted with the specimen
dimensions of 12.0 mm (D) × 3.0 mm (T) on a TA Instruments
DMA Q800 with compression mode from room temperature to
−90
C at a cooling rate of 5
C min−1. Morphologies of fracture
surfaces were studied on a Zeiss Supra 40 field-emission scanning
electron microscope (FESEM) at 15 kV. The fracture surfaces
were sputtered with a gold layer before observation. An Instron
5569 universal testing machine was employed to conduct the ten-
sile tests at ambient temperature in accordance with ASTM D412
standard. The data were processed and acquired with Bluehill
software. The Shore Type-A hardness test was performed on a
LAC-J durometer according to ASTM D2240 standard.
RESULTS AND DISCUSSION
Fabrication of Acrylo POSS-Modified LSR Composites
Acrylo POSS was incorporated into PDMS networks in this study
via hydrosilylation reaction between Si-H bond in HPDMS and
C=C bond in acrylo POSS, which is similar to the reaction
between HPDMS and VPDMS. To verify the hydrosilylation
reaction, 1H NMR and FT-IR spectrometers were used and the
spectra of acrylo POSS, HPDMS, and their mixture with Pt cata-
lyst after stirring for 2 h at room temperature were recorded as
shown in Figures 2 and 3, respectively. In Figure 2(c), the peak at
4.7 ppm assigned to Si-H in HPDMS can still be seen for the
mixture as the amount of Si-H group in HPDMS is in excess of
46996 (3 of 8)
HPDMS [g] Acrylo POSS [g] Si-H / C=C [mol/mol]
1.20 0 1.4
1.71 0.25 1.4
2.22 0.50 1.4
2.73 0.75 1.4
2.73 0 3.2
that of C=C group in acrylo POSS. While the peaks at between
5.5 and 6.5 ppm (assigned to CH=CH2 in acrylo POSS) vanished
completely and the new peaks at 2.3 and 1.1 ppm can be attrib-
uted to OCCH2CH2Si and OCCH2CH2Si after addition reaction.
The FT-IR spectra in Figure 3 could also provide clear and direct
evidence for the reaction. The strong stretching vibration band of
Si-H in HPDMS at 2153 cm−1 decreases significantly and the
bending vibration band of C=C in acrylo POSS at 1624 cm−1 dis-
appears in the spectrum of the mixture. Meanwhile, the charac-
teristic band of C=O groups in acrylo POSS at 1730 cm−1
remains in the spectrum. Therefore, it suggests that acrylo POSS
can be successfully linked to the PDMS networks. When more
acrylo POSS was added in vulcanized LSR composites, a stronger
peak at 1730 cm−1 could be seen in normalized FT-IR spectra
shown in Figure 4.
Thermal degradation behavior of LSR composites was studied by
heating 7 mg of cubic samples to 800
C under N2 atmosphere,
and the TGA results of LSR-0 and LSR-3 are presented in
Figure 5. The curves show that the addition of acrylo POSS does
not change the initial decomposition temperature obviously but
increases the residual weight percentage. To better understand
how the acrylo POSS could affect the thermal stability of LSR,
the surfaces and cross-sections of samples after TGA tests were
observed with SEM. The images in Figure 6 convey the differ-
ences between LSR-0 and LSR-3. As for LSR-0, the external and
cross-sectional surfaces are distinctly different on the particle size;
under direct heating the external fumed silica tends to aggregates
in Figure 6(a), while the internal fumed silica could maintain rel-
atively separate in Figure 6(b). The LSR-3 however has a more
continuous and denser structure on the surface in Figure 6(c). It
should be ascribed to the direct carbonization of chemically
incorporated acrylo POSS and altered network structure of LSR
composite. Thereafter, with the protection of exterior denser
layers, the crosslinked PDMS and POSS within the core area for
LSR-3 in Figure 6(d) experienced incomplete decomposition in
contrast to LSR-0 (Figure 6(b)). It well explains why their resid-
ual difference (12%) is much higher than the percentage of added
acrylo POSS (<1.5%).
Crosslink Structure Studies
To verify the crosslink density of the silicone rubber, extraction
and swelling experiments were conducted. As summarized in
Table II, the weight percentage of soluble fraction (Wsol%) and
degree of swelling (Dsw) in THF both decrease when more acrylo
POSS was introduced into the LSR composites. The LSR-3 has
the smallest Wsol% and Dsw among all specimens. It indicates
that acrylo POSS could increase the crosslink density of three
J. APPL. POLYM. SCI. 2018, DOI: 10.1002/APP.46996
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a O O
(a) H3C O O O CH3 (b) b d
a'
a H3C Si Si Si Si CH3 O O O
n m O Si c Si
H3C CH3 H3C H
OO
H3C CH3
O O
b Si OO Si O O
O
O O Si O O Si O
a O Si O
O Si O
O O
H2O O O
CDCl3 b
CDCl3
a+a' c d
b

8 6 4 2 0 8 6 4 2 0
Chemical Shift (ppm) Chemical Shift (ppm)

H3C
O
O
a H3C Si O
O
Si CH3
H3C Si
(c) CDCl3 H3C CH3
n
p Si
q Si CH3
RO H3C H
H3C b CH2 CH3 CH3
Si O O
g
R'O e c CH2
RO O O
O Si
Si
O f
H3C
Si O d O OR a
O Si O Si O
O O O Si CH3
R'O O
O O Si O O Si O OR'
RO O
Si Si O OR
O Si O
H3C
O O Si CH3
R'O
O O OR OR'
RO
Si b Si CH3
H3C
OR'
R'O
c g
f d e

8 6 4 2 0
Chemical Shift (ppm)
Figure 2. 1H NMR spectra of Acrylo POSS (a), HPDMS (b), and their mixture under catalysis of Pt in d-chloroform (c).

dimensional networks for LSR composites. The Shore Type-A Dynamic mechanical analysis is also an effective and indirect
hardness test results in Table II exhibit obvious improvement method to study the molecular structure of materials. The storage
when acrylo POSS is added into the matrix. It agrees well with moduli at room temperature for all LSR composite samples are
the change of crosslink density. summarized in Table II and the curves are shown in Figure S1

LSR-0
C=O
Transmittance (a. u.)

Acrylo POSS C=C

Transmittance (a. u.)

LSR-1

HPDMS C=C
Si-H
LSR-2

Acrylo POSS & HPDMS LSR-3

C=O
4000 3500 3000 2500 2000 1500 1000 500
-1 4000 3500 3000 2500 2000 1500 1000 500
Wavenumber (cm )
-1
Figure 3. FT-IR spectra of Acrylo POSS, HPDMS, and their mixture under Wavenumber (cm )
catalysis of Pt. Figure 4. FT-IR spectra of LSR with different contents of Acrylo POSS.

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Figure 5. TGA curves of LSR-0 and LSR-3 under nitrogen atmosphere.
(Supporting information). The crosslink density (ρ) of a silicone
rubber is proportional to its storage modulus in the rubbery pla-
teau according to the classic rubber elasticity theory. In spite of
the existence of fillers, it can be approximately concluded that the
LSR composites have higher crosslinking densities when more
acrylo POSS is introduced into the matrix.
Mechanical Properties and Morphological Study
To investigate the reinforcement effect of incorporated acrylo
POSS on mechanical properties of LSR composites, the tensile
tests were performed for all composite samples with different
weight fractions of acrylo POSS and control samples. Their typi-
cal tensile profiles are shown in Figure 7 and the data for modu-
lus, strength, and strain at break are presented in Table III.
Figure 6. Surface and cross-sectional SEM images of LSR-0 (a and b) and LSR-3 (c and d) samples after TGA tests.
46996 (5 of 8)
Consistent with the DMA results in Table II, the modulus and
strength are improved greatly upon the incorporation of acrylo
POSS, while the elongation at break descends slightly with acrylo
POSS increasing. This is due to that the incorporation of reactive
acrylo POSS forms tighter three-dimensional network, as verified
above, leading to enhanced modulus, strength, and rigidity. It is
noteworthy that only 1.5 phr of acrylo POSS could lead to a sig-
nificant increase of 66% for ultimate tensile strength, in contrast
to fumed silica only system in which a 100% increase of tensile
strength needs about 10 phr of fumed silica.2 It could be ascribed
to the smallest size of POSS as a silica and covalent bond with
PDMS. Although LSR-control sample without POSS has the
highest Young’s modulus, which is consistent with the report that
increasing the ratio of curing agent (HPDMS) to base (VPDMS)
could results in more rigid elastomers,23 however, its tensile
strength and elongation at break decrease dramatically. The dif-
ference on mechanical properties between LSR-control and LSR-
3 highlights the positive role of added acrylo POSS.
The morphologies for the fractured surfaces of LSR samples were
studied using SEM. Their representative cross-section images are
shown in Figures 8 and 9. When no acrylo POSS is added, the
facture surface of LSR-0 looks even and smooth in Figure 8
(a) and fumed silica aggregates evenly on the PDMS chains,
forming the worm-like networks in Figure 8(b). As more acrylo
POSS is incorporated, more fumed silica self-aggregates into
submicron-sized particles which should be pulled out from the
matrix and the worm-like networks could not be observed clearly,
especially for LSR-3. Obviously, the crosslink networks alter due
to the chemical incorporation of POSS, and the denser structures
beneath the aggregated particles are probably due to the strong
cohesion of fumed silica with POSS-incorporated PDMS chains.
In contrast to LSR-3, LSR-control shows distinct worm-like
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Table II. Physical Properties of Addition-Cured LSR Composites Table III. Mechanical Properties of Addition-Cured LSR Composites

Storage Young’s Tensile

modulusa modulus strength Elongation at
Samples Wsol% Dsw Hardness [MPa] Samples [MPa] [MPa] break [%]
LSR-0 11.7% 171% 32 1.20 LSR-0 0.60  0.02 1.38  0.05 134.1  5.4
LSR-1 6.0% 152% 40 2.20 LSR-1 1.26  0.04 1.78  0.14 114.7  9.7
LSR-2 3.5% 141% 51 3.23 LSR-2 2.51  0.03 2.33  0.27 104.4  13.5
LSR-3 3.0% 134% 59 4.02 LSR-3 3.19  0.04 2.29  0.22 84.0  9.9
LSR-Control 2.4% 128% 60 4.12 LSR-control 3.24  0.03 0.99  0.15 40.1  6.4
a
At 20
C.

2.5
LSR-0

2.0 LSR-1
LSR-2
LSR-3
Tensile Stress (MPa)

1.5
Control

1.0

0.5

0.0

-0.5
0 20 40 60 80 100 120 140
Tensile Strain (%)
Figure 7. Typical tensile curves for LSR composites.

Figure 8. SEM images of fracture surfaces of cured LSR samples: LSR-0 (a and b) and LSR-1 (c and d). [Color figure can be viewed at wileyonlinelibrary.com]

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Figure 9. SEM images of fracture surfaces of cured LSR samples: LSR-2 (a and b), LSR-3 (c and d) and LSR-Control (e and f). The black arrows indicate the
PDMS chains surrounded by fumed silica. [Color figure can be viewed at wileyonlinelibrary.com]

networks except the same agglutination of fumed silica. It indi- ACKNOWLEDGMENTS

cates that their network structures are different even though their This work was financially supported by Science and Engineering
crosslink densities are both increased. Therefore, the covalently Research Council (SERC), Agency for Science, Technology and
introduced acrylo POSS plays an important role on mechanical Research (A∗STAR) under Grant number R-284-000-135-305.
properties of LSR composites.

CONCLUSIONS
REFERENCES
In this work, addition-cured LSR composites strengthened by
commercial liquid acrylo POSS together with fumed silica fillers
were facilely fabricated. One of the major advantages for the liq-
uid acrylo POSS is that no solvent is required during the homo-
geneous mixing of fillers with silicones, and it surely promotes
the large-scale usage of POSS in silicone industry. More impor-
tantly, it is proved that acrylo POSS is covalently integrated into
the silicone rubber matrix, and largely increases the crosslink
density, and eventually causes significant enhancement on
mechanical properties, namely, higher modulus, tensile strength,
and hardness. In conclusion, the acrylo POSS could act as func-
tional and efficient nanofillers in producing high-quality LSR
composites.
1. Zhang, M.; Denes, I.; Buchmeiser, M. R. Macromol. Mater.
Eng. 2016, 301, 337.
2. Ansarifar, A.; Lim, B. Y. J. Rubb. Res. 2006, 9, 140.
3. Yang, H.-S.; Park, E.-S. Macromol. Mater. Eng. 2006,
291, 621.
4. Zhang, W.; Müller, A. H. E. Prog. Polym. Sci. 2013, 38,
1121.
5. Zhang, W.; Camino, G.; Yang, R. Prog. Polym. Sci. 2017,
67, 77.
6. Sun, Y.; He, C. Macromolecules. 2013, 46, 9625.
7. Zhou, X.; Fan, X.; He, C. Macromolecules. 2016, 49, 4236.

46996 (7 of 8) J. APPL. POLYM. SCI. 2018, DOI: 10.1002/APP.46996

ARTICLE WILEYONLINELIBRARY.COM/APP

8. Li, Y. C.; Mannen, S.; Schulz, J.; Grunlan, J. C. J. Mater.
Chem. 2011, 21, 3060.
9. Wang, X.; Song, L.; Yang, H. Y.; Xing, W. Y.; Kandola, B.;
Hua, Y. J. Mater. Chem. 2012, 22, 22037.
10. Chen, D.; Yi, S.; Wu, W.; Zhong, Y.; Liao, J.; Huang, C.;
Shi, W. Polymer. 2010, 51, 3867.
11. Chen, D.; Nie, J.; Yi, S.; Wu, W.; Zhong, Y.; Liao, J.;
Huang, C. Polym. Degrad. Stab. 2010, 95, 618.
12. Chen, D.; Yi, S.; Fang, P.; Zhong, Y.; Huang, C.; Wu, X.
React. Funct. Polym. 2011, 71, 502.
13. Chen, D.; Liu, Y.; Huang, C. Polym. Degrad. Stab. 2012,
97, 308.
14. Zhang, Y.; Mao, Y.; Chen, D.; Wu, W.; Yi, S.; Mo, S.;
Huang, C. Polym. Degrad. Stab. 2013, 98, 916.
15. Zhao, M.; Feng, Y.; Li, Y.; Li, G.; Wang, Y.; Han, Y.;
Sun, X.; Tan, X. J. Macromol. Sci., Pure Appl. Chem. 2014,
51, 639.
16. Shi, Y.; Liu, Y.; Qu, Y.; Zhang, D.; Huang, G. J. Polym. Res.
2013, 20, 245.
17. Joshi, V.; Srividhya, M.; Dubey, M.; Ghosh, A. K.;
Saxena, A. J. Appl. Polym. Sci. 2013, 130, 92.
18. Bai, H.; Huang, C.; Jun, L.; Li, H. J. Appl.Polym. Sci. 2016,
133, 43906.>
19. Zhang, Y.; Li, Y.; Zheng, J.; Guo, H.; Guan, X.; Lu, M.;
Wu, K.; Liang, L. J. Appl. Polym. Sci. 2015, 132, 42187.
20. Shi, Y.; Gao, X.; Zhang, D.; Liu, Y.; Huang, G. RSC Adv.
2014, 4, 41453.
21. Zhang, D.; Shi, Y.; Liu, Y.; Huang, G. RSC Adv. 2014, 4,
41364.
22. Liu, Y.; Shi, Y.; Zhang, D.; Li, J.; Huang, G. Polymer. 2013,
54, 6140.
23. Campbell, D. J.; Beckman, K. J.; Calderon, C. E.;
Doolan, P. W.; Ottosen, R. M.; Ellis, A. B.; Lisensky, G. C.
J. Chem. Educ. 1999, 76, 537.

46996 (8 of 8) J. APPL. POLYM. SCI. 2018, DOI: 10.1002/APP.46996