Novel synergistic flame-retardant system of Mg–Al–Co–LDHs/DPCPB

for ABS resins

Hongbing Mo, Liping Xu, Tao Zhou
Hunan Provincial Key Laboratory of Efficient and Clean Utilization of Manganese Resources, College of Chemistry and
Chemical Engineering, Central South University, Changsha 410083, People’s Republic of China
Correspondence to: (E - mail: zhoutao@csu.edu.cn)

ABSTRACT: Acrylonitrile-butadiene-styrene (ABS) resins are widely used in many sectors of the industry due to excellent mechanical
properties, low temperature resistance, heat resistance, and chemical resistance. However, its flammability constitutes a key limitation
in their applications. Consequently, development of flame-retarding ABS resins is imperative. Herein, we report a novel synergistic
system composed of Mg–Al–Co–layered double hydroxides (LDHs) prepared via a co-precipitation method, and [4-(diphenoxy-phos-
phorylamino)-6-phenyl-[l,3,5] triazin-2-y1]-phosphoramidic acid diphenyl ester (DPCPB), a novel intumescent flame retardant. The
properties of the as-prepared LDHs/DPCPB/ABS composites are evaluated using standard combustion performance tests including
limiting oxygen index (LOI) and vertical burning test (UL-94). Novel ABS resins with the composition of ABS/DPCPB 5 100/25 and
ABS/DPCPB/LDHs 5 100/2l/4 exhibit higher LOIs, 23.9 and 24.7, respectively, compared to 18.1 for the pure ABS. Meanwhile, they
meet the V-2 and A-1 level, respectively, in UL-94 tests. Moreover, the prepared composites exert flame-retarding effects in gas phase
and condensed phase simultaneously. Our results reveal synergistic effects between Mg–Al–Co–LDHs and DPCPB for the flame retar-
dation of ABS resins. VC 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46319.

KEYWORDS: flame retardance; synthesis and processing techniques; thermogravimetric analysis

Received 19 July 2017; accepted 1 February 2018

DOI: 10.1002/app.46319

INTRODUCTION
Engineering thermoplastics composites of acrylonitrile-
butadiene-styrene (ABS) are popular due to good mechanical
properties, chemical resistance, and easy processing. However,
the flammability of ABS resins is a serious concern for its appli-
cations in automobile industry, electric appliance, and office
supply. Moreover, ABS resins generate smoke and toxic gases in
great quantities during burning, which brings another potential
risk for its application.1–3 Therefore, it is imperative to improve
the flame retardancy and smoke suppression of ABS resins.
Halogen-containing compounds, such as decabromodiphenyl
oxide, octabromobiphenyl oxide, tetrabromobis-phenol, and 1,2-
bis(2,4,6-tribromophenoxy)ethane, are the most effective flame
retardants for ABS. Nevertheless, the potential risk of generating
toxic gases during combustion violates new environmental require-
ments.4,5 Consequently, some halogen-containing compounds are
forbidden by law.6,7 In terms of smoke suppression, antimony triox-
ide has been conventionally adopted as co-additives, bringing about
synergistic effects with halogen-containing materials.
Organic phosphates are heavily touted as one of the most
promising candidates replacing halogen-containing compounds.
Continuing efforts have been made for its application in ABS
resins. Triphenyl phosphate (TPP) with various epoxy resins
was incorporated into ABS, resulting in a limiting oxygen index
(LOI) value of 38.8 However, most TPPs are in liquid or resin
state, leading to notorious handling problems. Furthermore, the
high volatility of these compounds is annoying during loading.
More and more attention has been turned to nitrogen–phos-
phorus (P–N) compounds, which are also known as intumes-
cent flame retardants (IFR), because of the thermal stability and
P–N synergistic effects.9–12 Nguyen13 synthesized various P–N
compounds based on phosphoramidates and demonstrated that
the addition of these compounds can effectively improve the
thermal stability and char yields of ABS resins. However, there
is still a huge gap between ABS employing P–N compounds as
a single flame-retarding component and the requirement of
UL-94V-0 level.14,15
To improve the smoke suppression of ABS resins, inorganic
materials such as magnesium hydroxide,16,17 antimony triox-
ide18 have been intensively investigated as flame retardants
(FRs). Layered double hydroxides (LDHs), also known as
hydrotalcites, have drawn increasing attention because of its
composition flexibility, smoke suppression effect, and decent

C 2018 Wiley Periodicals, Inc.

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Scheme 1. Reaction formula of DPCPB synthesis
mechanical properties.19–23 A significant reduction of peak heat
release rate was found when MgAl or ZnMgAl LDHs was intro-
duced into ABS resins as FRs. Moreover, ZnMgAl LDHs pro-
vided a higher LOI value and a longer combustion time
compared to MgAl LDHs.24,25 As a novel IFR, [4-(diphenoxy-
phosphorylamino)-6-phenyl-[l,3,5] triazin-2-y1]-phosphorami-
dic acid diphenyl ester (DPCPB) was firstly synthesized by Tera-
moto and coworkers,26 while the flame retarding efficiency of
this compound in ABS resins has not been studied yet. This is
the gap that this paper intends to fill by developing a novel syn-
ergistic ABS resin system composed of Mg–Al–Co–DBS–LDHs
and DPCPB.
EXPERIMENTAL
Materials
All the starting materials and solvents are commercially available
and were applied without further purification. Reagent grade
benzoguanamine was purchased from Dingmiao Chemistry
(Shanghai, China). Diphenyl chlorophosphate (DPCP) of C.R.
grade was obtained from Department of Labor (Beijing), Chem-
ical Technology Co., Ltd. Mg(NO3)2
6H2O, Al(NO3)3
9H2O,
and Co(NO3)2
6H2O were supplied by Sinopharm Chemical
Reagent Co., Ltd. (Ningbo, China). The ABS resin (Product
number: PA-757) was obtained from Qimei Industry Stock Co.,
Ltd. (Taiwan, China).
Synthesis of DPCPB
The synthesis method of DPCPB was described below26: the
mixture of 0.05 mol benzoguanamine (C9H9N5) and 0.1 mol
triethylamine (Et3N) was dissolved in 200 mL dry tetrahydrofu-
ran (C4H8O, THF) and the solution was then transferred into a
three-necked flask equipped with a temperature controller, a
Figure 1. FTIR spectrum of DPCPB after purification. [Color figure can
be viewed at wileyonlinelibrary.com]
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reflux condenser, and a mechanical stirrer. 0.1 mol DPCP
(C12H10ClO3P, DPCP) was dissolved in 30 mL dry THF and
then the solution was added dropwise over 30 min into the
flask which was kept at 0 8C with vigorous mechanical stirring.
Then, the mixture was warmed up to 65 8C and refluxed for
10–12 h. Salt of Et3N
HCl was removed via filtration. The crude
product was obtained after evaporation of the filtrate. A purifi-
cation process was conducted in 60–65% aqueous alcohol for
15–20 min ultrasonically and then product of niveous powder is
ready for characterization and testing. The reaction equation is
presented in Scheme 1. The synthesized product was confirmed
to be DPCPB by FTIR, see Figure 1.
Synthesis of Mg–Al–Co–LDHs
The sodium dodecyl benzene sulfonate (SDBS) modified Mg–
Al–Co–LDHs (molar ratio of Mg:Al:Co 5 2:1:0.5) were synthe-
sized via a single step co-precipitation method. Firstly, 0.1
mol L21 SDBS (100 mL) was added in a three-necked flask
equipped with a temperature controller, a reflux condenser, and
a mechanical stirrer. Then 0.25 mol L21 metal ion solution
(150 mL) was mixed with 0.56 mol L21 sodium hydroxide
(150 mL), and the mixture was added dropwise into the flask
containing the SDBS with continuous stirring at 55 8C, followed
by another 1 h of mechanical stirring and 12 h of aging. The
suspensions were filtered, and filter cake was washed with dis-
tilled water, and then dried at 60 8C in vacuum oven. The dried
samples were ground to powders.
Preparation of ABS Composites
Firstly, a certain ratio, as shown in Table I, of ABS resin and FR
was mechanically mixed at a high-speed kneader. Then the mix-
ture was added into a twin-screw extruder for extrusion and
granulation. The temperature of the extruder was controlled
according to Table II, which is dictated by the melting tempera-
ture of ABS resins. Finally the composites after drying were pre-
pared as a standard spline for further tests by an injection
molding machine at temperature (200–225 8C) and high
Table I. Recipes of Different ABS Composites
ABS (g) DPCPB (g) MgAAlACoALDHs (g)
1000 0 0
1000 0 40
1000 250 0
1000 300 0
1000 210 40
1000 260 40
J. APPL. POLYM. SCI. 2018, DOI: 10.1002/APP.46319
ARTICLE WILEYONLINELIBRARY.COM/APP
Table II. Temperature Controlling Protocol of the Extrusion Process
Sections 1 2
Temperature (8C) 190 190
pressure (30–50 MPa). Then, the composites were cooled at
room temperature for 25 s.
RESULTS AND DISCUSSION
Characterization of DPCPB
Figure 1 shows the FTIR spectra of the purified DPCPB. The
characteristic absorption peaks at 1569.7l, 1542.23, and 808.21
(triazine structure); 1243.36 and 1207.93 (P@O); 1024.28 and
975.24 cm21 (PAOAPh) are found. Moreover, the peaks
appearing around 3381.29 cm21 can be assigned to the NAH
bond. The absorption at 3148.04 cm21 corresponds to the
ANHA. Finally, the absorption peak at 1089.92 cm21 mirrors
the PAN. These results indicate that the DPCPB is successfully
synthesized with a high purity.
1
H NMR spectrum of the purified DPCPB is showed in Figure
2. One of the representative peaks appears at 3.32 ppm is the
resonance of CD3OD (solvent used in analysis of 1H NMR spec-
trum). The other peaks from 7.07 to 7.69 ppm are ascribed to
chemical shift of the PhAH. The peak at 8.18 ppm is attributed
to the resonance of the PANHAH. Combined, 1H NMR and
infrared absorption spectra support that the synthesized product
is DPCPB.
Figure 2. 1H NMR spectrum of DPCPB after purification. [Color figure can be viewed at wileyonlinelibrary.com]
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3 4 5 Handpiece
195 200 215 195
X-ray Diffraction and SEM Images of the MgAAlACoALDHs
X-ray Diffraction (XRD) measurements are performed to char-
acterize the composition of the synthesized powder, as shown in
Figure 3. The peak profile is consistent with that of the
MgAAlACoALDHs.27 Moreover, the XRD patterns clearly
exhibit a layered structure without impurity, indicating that the
synthesized MgAAlACoALDHs have a steady and single crystal
structure.
In the single step co-precipitation method, it is difficult to con-
trol the crystallization process of MgAAlACoALDHs particles,
although the size distribution and grain growth can be con-
trolled. Therefore, MgAAlACoALDHs particles are irregular
flakes with the size of about 200–350 nm and agglomeration
among particles is observed before the hydrothermal treatment,
as showed in Figure 4(a). Hydrothermal treatment is necessary
to achieve regular, narrow size distribution, and monodisperse
MgAAlACoALDHs particles, because the hydrothermal treat-
ment facilitates crystallization, and reduces particle agglomera-
tion. Figure 4 compares the morphology of MgAAlACoALDHs
particles before and after the hydrothermal treatment. It can be
seen that MgAAlACoALDHs particles have a monodisperse
hexagonal flaky structure with a size of about 350–500 nm.
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Figure 3. XRD pattern of the MgAAlACoALDHs.
Moreover, agglomeration among particles decreases remarkably
after the hydrothermal treatment at 140 8C for 15 h.
Dispersion of MgAAlACoALDHs in Composites
Dispersion of inorganic FRs in substrates influences significantly
the mechanical and fire resistant properties of the composites.
Large inorganic FRs particles tend to concentrate stress in the
substrate, degrading its shock resistant performance, while small
particles incline to gather forming agglomerates spontaneously,
imposing difficulty on blending and dispersion.28 Nevertheless,
hydrotalcites, namely LDHs, can be dispersed in the substrate in
various forms due to its special laminated structure. Mg–Al–
Co–LDHs are used as a synergistic FR and its dispersion state
in the ABS composites is schematically shown as Figures 5 and
6. It is seen that the impact section of pure ABS is smooth [Fig-
ure 6(a)], implying excellent compatibility of two phases in ABS
resin. This is the reason why ABS resin possesses excellent
impact resistance. The impact section is free of fibrous region,
suggesting that the fracture of ABS resin belongs to brittle frac-
ture. For ABS/DPCPB, a distinct lamellar structure appears in
the impact section and there are interfaces at the edge of
Figure 4. SEM image of MgAAlACoALDHs. (A) Mg-Al-Co-LDHs particles before hydrothermal treatment (B) Mg-Al-Co-LDHs particles after hydro-
thermal treatment.
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Figure 5. Dispersion state MgAAlACoALDHs in the ABS composites.
(A) intercalated structure, (B) exfoliated layered structure. [Color figure
can be viewed at wileyonlinelibrary.com]
lamellar structure [Figure 6(b)]. The impact section of ABS/
DPCPB/LDHs is similar to that of ABS/DPCPB [Figure 6(c)].
Compared with pure MgAAlACoALDHs and ABS resins, ABS/
DPCPB/LDHs composites show small-angle direction changes
in the diffraction peak of the MgAAlACoALDHs (003) in XRD
spectrums, implying that the intercalated structure is
formed between ABS chains and MgAAlACoALDHs (Figure
7). Meanwhile, no diffraction peaks at other angles can be
observed for MgAAlACoALDHs, indicating that the exfoliated
layered structure is formed between the ABS chains and
MgAAlACoALDHs. This means that the prepared trimetal
hydroxides are uniformly dispersed in the substrate, thereby the
FR function can be fully leveraged to the greatest extent and the
negative effect of inorganic retardant particles on mechanical
properties of composites are suppressed at the same time.
Flame-Retarding Properties
The flame-retarding efficiency of ABS composites was evaluated
by LOI and vertical burning test (UL-94). The results are shown
in Table III. Samples with dimensions of 120 3 6 3 3 mm3
were tested for their LOI values according to D2863-77. The
UL-94 test was conducted using samples with dimensions of
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Figure 6. SEM images of different ABS composites. (A) pure ABS; (B) ABS/DPCPB; (C) ABS/DPCPB/Mg-Al-Co-LDHs. [Color figure can be viewed at
wileyonlinelibrary.com]

127 3 12.7 3 3 mm3 according to ASTMD635-77. Compared
with 18.1 for pure ABS, the LOI value of ABS/LDHs ratio of
100/4 is 23.3, and the UL-94 value of the same sample is V-2
level. With the ABS/DPCPB ratio of 100/25, the LOI value of
the corresponding composites was improved from 18.1 (pure
ABS) to 23.9 and the V-2 level was obtained in terms of
the UL-94 test. The LOI value is 26.4 and the UL-94 is V-1
level for the ABS/DPCPB ratio of 100/30. Regarding ABS/
DPCPB/LDHs with a mass ratio 100/21/4, the LOI value
increases to 24.7 and the UL-94 is V-1 level; the perfor-
mance is superior to ABS/DPCPB with a mass ratio 100/25.
The performance can be improved further (the LOI value is
27.1 and the UL-94 is V-0 level) for the ABS/DPCPB/LDHs
composite with a ratio of 100/26/4. The results imply that

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Figure 7. XRD pattern of different composites. (A) Mg-Al-Co-LDHs; (B) Figure 8. TGA curves of different composites. [Color figure can be viewed
pure ABS; (C) ABS/DPCPB/Mg-Al-Co-LDHs. [Color figure can be viewed at wileyonlinelibrary.com]
at wileyonlinelibrary.com]

The DTG curves of the pure ABS resin and its different compo-
the synergistic FR system achieves higher flame resistance
sites are shown in Figure 9. Curve 1 is the weight-loss rate of
performance in the LOI test, and produces less smoke
the pure ABS resin, revealing that the thermal stability of ABS
during the UL-94 test due to the existence of is excellent and there is not obvious thermal decomposition
MgAAlACoALDHs. Comparison with literature reports25,29 before 350 8C. The weight-loss rate of the pure ABS resin
indicates that the newly-prepared ABS/DPCPB/LDHs compo- increases significantly as the temperature increases from 350 to
sites show decent performance. 420 8C and the highest weight-loss rate of 220.8%/min is
observed at 420 8C.
Thermal Stability of Composites
Thermal decomposition of ABS composites with different for- Compared with the pure ABS resins, the initial thermal decom-
mula was characterized by TGA. The TGA was carried out in an position temperature of ABS/DPCPB composites (Curves 2 and
N2 atmosphere at a heating rate of 10 8C/min, as showed in Fig- 4 in Figure 9) is advanced. However, the weight-loss rate
ure 8. The initial temperature of thermal decomposition of pure increases slowly with increasing temperature, and achieves its
ABS resin is around 330 8C. The rate of decomposition is the maximum (–1.7%/min for ABS/DPCPB 5 100/25 and 22.9%/
min for ABS/DPCPB 5 100/30) at 320 8C. This phenomenon
fastest at 400–475 8C and the decomposition is nearly completed
can be understood as follows. Triazine in DPCPB is thermally
at 500 8C. 95.28% of pure ABS resin is decomposed during the
decomposed generating inert gases (NOx), thus diluting the
test. When the FR composite formula was ABS/DPCPB 5 100/
oxygen concentration near the heated area. Following that, the
25, ABS/DPCPB/LDHs 5 100/21/4, the initial thermal decompo-
weight-loss of ABS/DPCPB composites is mainly due to thermal
sition temperature was 250 and 225 8C, respectively. The
decomposition, and the weight-loss rate achieves another
decrease in the initial decomposition temperature is attributed
to the presence of the novel IFR DPCPB and LDHs. The prod-
ucts of thermal decomposition are mainly inert gases such as
nitrogen compounds. After thermal decomposition, the formula
of residual carbon yields was 11.7 and 12.3%, respectively, sug-
gesting that the addition of DPCPB effectively increase residual
carbon yields after combustion. Moreover, the addition of
LDHs may have an excellent synergistic effect with DPCPB.

Table III. Flame-Retarding Properties of Different Composites

ABS (g) DPCPB (g) LDHs (g) LOI (%) UL-94

1000 0 0 18.1 —
1000 0 40 23.3 V-2
1000 250 0 23.9 V-2
1000 210 40 24.7 V-1
1000 300 0 26.4 V-1
Figure 9. DTG curves of different composites. [Color figure can be viewed
1000 260 40 27.1 V-0 at wileyonlinelibrary.com]

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maximum value (–18.15%/min for ABS/DPCPB 5 100/25 and
213.96%/min for ABS/DPCPB 5 100/30) near 422 8C.
For ABS/DPCPB/MgAAlACoALDHs composites with the same
adding amount of FRs, the initial thermal decomposition tempera-
ture and the maximum value of weight-loss rate decrease compared
with the pure ABS resins, as showed in Curve 3 and 5 in Figure 9.
The weight-loss rate achieves the maximum value (A1.14%/min for
ABS/DPCPB/LDHs 5100/21/4 and A2.16%/min for ABS/DPCPB/
LDHs 5100/26/4) at 270 8C. This is attributed to the volatilization
of crystal water and pyrolysis of anion stored in the layers of LDHs.
With further increasing the temperature above 270 up to 450 8C,
more crystal water and anions among the layers of LDH would vola-
tilize and pyrolyze, respectively. Compared with the pure ABS resin,
the weight-loss rate achieves another maximum value (–16.9%/min
for ABS/DPCPB/LDHs 5 100/21/4 and 211.8%/min for ABS/
DPCPB/LDHs 5 100/26/4) near 430 8C.
CONCLUSIONS
In this study, we introduced the IFR DPCPB and the smoke suppres-
sant MgAAlACoALDHs to improve the flame retardancy for ABS
resins. Compared with pure ABS resins, the ABS/DPCPB composite
with a mass ratio of 100/25 showed a higher LOI value (23.9 vs.
18.1) and a V-2 level in UL-94 test. By adding MgAAlACoALDHs
powders into ABS/DPCPB composite, the LOI is further increased
to 24.7 and the V-1 level is achieved in the UL-94 test. This study
suggests that MgAAlACoALDHs and DPCPB have a synergistic
effect on flame retardancy of ABS resins.
ACKNOWLEDGMENTS
The authors acknowledge with gratitude for financial support of
the Hunan Provincial Science and Technology Plan Project, China
(no.2016TP1007) and National Natural Science Foundation of
China (no. 21176266).
REFERENCES
1. Xu, S.; Zhang, L.; Lin, Y.; Li, R.; Zhang, F. J. Phys. Chem.
Solids. 2012, 73, 1514.
2. Lim, K. S.; Bee, S. T.; Sin, L. T.; Tee, T. T.; Ratnam, C. T.;
Hui, D.; Rahmat, A. R. Compos. Part B: Eng. 2016, 84, 155.
3. Alaee, M.; Arias, P.; Sj€
odin, A.; Bergman, A. Environ. Int.
2003, 29, 683.
4. Wang, S.; Hu, Y.; Zong, R.; Yang, T.; Chen, Z. Appl. Clay
Sci. 2004, 25, 49.
5. Prieur, B.; Meub, M.; Wittemann, M.; Klein, R.; Bellayer, S.;
Fontaine, G.; Bourbigot, S. Polym. Degrad. Stab. 2016, 127, 32.
46319 (7 of 7)
6. Mitan, N. M. M.; Brebu, M.; Bhaskar, T.; Muto, A.; Sakata,
Y. J. Mater. Cycles Waste Manag. 2007, 9, 56.
7. Czegeny, Z.; Jakab, E.; Blazs
o, M.; Bhaskar, T.; Sakata, Y. J.
Anal. Appl. Pyrolysis 2012, 96, 69.
8. Lee, K.; Kim, H.; Bae, J.; Yang, J.; Hong, S. Polymer 2002,
43, 2249.
9. Peng, H.; Zhou, Q.; Wang, D.; Chen, L.; Wang, Y. J. Ind.
Eng. Chem. 2008, 14, 589.
10. Xie, F.; Wang, Y.; Yang, B.; Liu, Y. Macromol. Mater. Eng.
2006, 291, 247.
11. Jun, W.; Yi, J. S.; Cai, X. F. J. Appl. Polym. Sci. 2011, 120,
968.
12. Wu, N.; Lang, S. Polym. Degrad. Stab. 2016, 123, 26.
13. Nguyen, C.; Kim, J. Polym. Degrad. Stab. 2008, 93, 1037.
14. Nguyen, C.; Kim, J. Macromol. Res. 2008, 16, 620.
15. Pang, X. Y.; Tian, Y.; Weng, M. Q. Polym. Compos. 2015, 36,
1407.
16. Wu, N. J.; Xiu, Z. X.; Du, J. Y. J. Appl. Polym. Sci. 2017,
134, DOI 10.1002/app.45008
17. Chen, Y.; Zhou, T.; Fang, H.; Li, S.; Yao, Y.; Fan, B.; Wang,
J. Particuology 2016, 24, 177.
18. Petsom, A.; Roengsumran, S.; Ariyaphattanakul, A.;
Sangvanich, P. Polym. Degrad. Stab. 2003, 80, 17.
19. Rahmanian, O.; Maleki, M. H.; Dinari, M. J. Phys. Chem.
Solids. 2017, 110, 195.
20. Mallakpour, S.; Dinari, M.; Hatami, M. J. Therm. Anal. Cal-
orim. 2015, 120, 1293.
21. Mallakpour, S.; Dinari, M. Prog. Org. Coat. 2014, 77, 583.
22. Mallakpour, S.; Dinari, M. J. Therm. Anal. Calorim. 2015,
119, 1123.
23. Dinari, M.; Momeni, M. M.; Bozorgmehr, Z.; Karimi, S. J.
Iran. Chem. Soc. 2017, 14, 695.
24. Wang, D.-Y.; Das, A.; Costa, F. R.; Leuteritz, A.; Wang, Y.-
Z.; Wagenknecht, U.; Heinrich, G. Langmuir 2010, 26,
14162.
25. Zhang, M.; Ding, P.; Qu, B. Poly. Compos. 2009, 30, 1000.
26. Teramoto, M; Ohnishi, H.; Horita, H. JP2000344788A,
2000.
27. Wang, M.; Bao, W. J.; Wang, J.; Wang, K.; Xu, J. J.; Chen,
H. Y.; Xia, X. H. Sci. Rep. 2014, 4, 6606.
28. Owen, S. R.; Harper, J. F. Polym. Degrad. Stab. 1999, 64,
449.
29. Mallakpour, S.; Dinari, M.; Hatami, M. RSC Adv. 2014, 4,
42114.
J. APPL. POLYM. SCI. 2018, DOI: 10.1002/APP.46319