Progress in Organic Coatings 88 (2015) 283–292

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Progress in Organic Coatings

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

Synthesis and characterization of flame retardant hyperbranched

polyurethanes for nano-composite and nano-coating applications
Rasmika H. Patel, Kaushal S. Patel ∗
Department of Materials Science, Sardar Patel University, Vallabh Vidyanagar, Gujarat, India

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

Article history: Flame retardant hyperbranched polyurethanes were prepared by reacting phosphorous containing triol,
Received 25 August 2014 tris(bisphenol-A) mono phosphate, castor oil, and polyethylene glycol with different diisocyanates like
Received in revised form 17 June 2015 TDI, IPDI and HMDI via A2 +B3 method. In this method A2 reactants were diisocyanates along with castor
Accepted 9 July 2015
oil and polyethylene glycol whereas phosphorous containing triol was used as B3 reactant and dibutyltin
Available online 6 August 2015
dilaurate (DBTDL) was used as catalyst. Synthesized polyurethans were characterized by gel-permeation
chromatography (GPC), elemental analysis, Fourier transform infrared spectroscopy (FTIR) and 1 H NMR
Keywords:
spectroscopic techniques. Neat polyurethanes were used for preparing films. Nano-clay composites were
Hyperbranched polyurethanes
Nano-composites
prepared with various concentration of organomodified montmorillionite nano-clay. Flame retardant,
Nano-coatings Thermal and mechanical properties of these hyperbranched polyurethanes and their nano-composites
Flame retardant were found out. The polyurethanes and their formulations with nano-clay were also used for the coating
Thermal and mechanical properties of mild steel panels. Scratch, pencil, and impact hardness, flexibility and adhesion properties of coated
panels were also determined. Observations show an increase in the scratch hardness and flexibility with
the introduction of clay. All the coatings show excellent chemical resistance properties compare to their
linear counterpart.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction retardant by the use of phosphorous, halogen, nitrogen and boron

During the last few years, there is a continuous search of
advanced polymeric materials for coating applications which
results in the development of non-linear hyperbranched polymers
[1]. Due to their unique structures, a wide range of properties are
observed in the end products. Different types of hyperbranched
polyurethanes (HBPUs) having high solubility with high glossy, and
flexible coatings are reported in literature [2]. Literature surveys
show that most of the hyperbranched based structures are non-
flame retardant. In this study attention has been made to synthesize
flame retardant hyper branched polyurethanes by incorporating
phosphorus moiety into the branched structure. With the presence
of more number of end groups offering high crosslinking possibil-
ities, use of these polymers in coatings improve the appearance
as well as properties like scratch hardness, adhesion, flexibil-
ity, water resistance etc. These types of hyperbranched polymers,
for certain specific coating applications can also be made flame
∗ Corresponding author.
E-mail addresses: rasmi29@yahoo.com (R.H. Patel),
kaushal patel2005@yahoo.com (K.S. Patel).
based monomers [3]. Therefore, it was thought to prepare flame
retardant hyperbranched polyurethanes using phosphorous con-
taining aromatic monomer. The combination of phosphorous based
aromatic moiety with aliphatic castor oil and polyethylene glycol
will maintain balance between various properties required for the
development of an effective coatings. As the thermal degradation or
burning of halogen based compounds release toxic gases [4] most
of the users have turned toward phosphorous based compounds
which are preferred for their less toxic and high char forming char-
acteristics during burning [5].
Present work deals with the synthesis of phosphorous contain-
ing HBPUs for the development of flame retardant coating materials
by reacting castor oil, conventional polyethylene glycol (PEG) and
phosphorous containing triol tris(bisphenol-A) mono phosphate
with different types of diisocyanates and characterized by various
chemical and instrumental techniques. Thermal, mechanical and
flame retardant properties of the hyperbranched polyurethanes
have been found out. Organo-modified nano-clay in various con-
centrations have been used with HBPUs to develop nano-clay
composites and coatings. Various properties of the nano-clay com-
posites and coatings were found out and compared with the neat
HBPUs.

http://dx.doi.org/10.1016/j.porgcoat.2015.07.007
0300-9440/© 2015 Elsevier B.V. All rights reserved.
284 R.H. Patel, K.S. Patel / Progress in Organic Coatings 88 (2015) 283–292

Fig. 1. Synthesis of hyperbranched flame retardant polyurethanes.

2. Experimental from Aldrich and were used without further purification.

2.1. Materials
The reagents, polyethylene glycol, phosphorous oxy-
chloride (POCl3 ), N,N-dimethyl aniline, toluene diisocynate
(TDI), isophorone diisocynate (IPDI), hexamethylene diiso-
cynate (HMDI), dibutyl tin dilaurate (DBTDL) were procured
Montmorillonite-clay (MMT) was received from Fluka. Bisphenol-
A and polyethylene-glycol (PEG-M.W. 392) were received from
Mark. Castor oil was obtained from the local market having
the hydroxyl value of 153. Solvent methyl ethyl ketone (MEK)
and xylene (XL) were used after distillation. Mild steel panels
(75 mm × 150 mm × 0.82 mm) were used as substrate for all the
coating applications.
 R.H. Patel, K.S. Patel / Progress in Organic Coatings 88 (2015) 283–292 285

a three neck round bottom reaction flask with constant stirring at

room temperature. Excess amount of toluene diisocynate (6.0 mol)
in xylene/MEK solvent mixture was mixed with dibutyl tin dilau-
rate (DBTDL) (0.005 mol) and the mixture was added drop-wise in
to the reaction flask at room temperature over a period of 30 min.
The reaction was heated at 60 ◦ C for 4 h under continuous stirring to
obtain a viscous liquid of NCO terminated urethane pre-polymer.
This pre-polymer was used as such for further reaction in step II
to react with phosphorous based triol in presence of unreacted
diisocyanate.

Fig. 2. XRD images of (a) unmodified MMT clay (b) modified MMT clay.
2.2. Synthesis of phosphorous containing triol
The phosphorous containing triol, tris (bisphenol-A) mono
phosphate (TBAMP) was synthesized by reacting bisphenol-A
(3 mol) and phosphorous oxychloride (1 mol) in presence of a
catalyst N,N-dimethyl aniline (0.01%) according to the reported
method [6]. This triol was used to react with polyurethane-
pre-polymer (step-I) to prepare hyperbranched polyurethanes
(step-II).
2.3. Synthesis of hyperbranched polyurethanes
2.3.1. Step-I
Castor oil (1.0 mol) and polyethylene glycol (1.0 mol) and 50 ml
solvent mixture of xylene/methyl ethyl ketone (1:4) were taken in
2.3.2. Step-II
The solid triol (TBAMP) was dissolved in xylene/MEK mixture
(1:4). The dilute solution (5%) of triol (TBAMP, 2 mol) was added
in a drop-wise manner into the reaction mixture of pre-polymer
(step-I) with continuous stirring at 10 ◦ C temperature for 1 h. After
the completion of addition, the reaction was heated at 60 ◦ C for 2 h.
Reaction conditions were controlled strictly to prevent the gelation
of the product during the reaction. The excess solvent was removed
from the end product by vacuum distillation to get a flame retardant
hyperbranched polyurethane (HBPU-1).
Other two flame retardant hyperbranched polyurethanes
HBPU-2 and HBPU-3 were prepared by reacting two different diiso-
cyanates, IPDI and HMDI respectively with triol using the above
method. Fig. 1 shows the reaction steps involved in the synthesis
of HBPUs. The physical properties of the polyurethanes are given
in Table 1.

Fig. 3. Flow-sheet diagram of the steps involved in the fabrication of nano-composites and nano-coating starting from the synthesis of pre-polymer.

Table 1
Reaction conditions and physical properties of hyperbranched polyurethanes.

Systems Intrinsic viscosity  Number average Weight average Elemental analysis (%)
dl/gm molecular weight molecular weight

Mn Mw C H N

HBPU-1 0.34 2002 7038 66.4 5.9 4.2

(67.9) (6.7) (4.8)
HBPU-2 0.31 2140 8924 68.2 7.0 3.9
(68.5) (7.8) (4.5)
HBPU-3 0.32 1927 9780 65.9 7.1 4.1
(66.6) (7.9) (4.9)

Calculated values are listed in parenthesis.

286 R.H. Patel, K.S. Patel / Progress in Organic Coatings 88 (2015) 283–292

Table 2
Thermal properties of neat hyperbranched polyurethane and hyperbranched polyurethane nano-clay composites.

Systems % Weight loss from TGA in air (◦ C) IPDT (◦ C) Activation Energy Ea (kJ mol−1 ) Char yield at 600 ◦ C (%)

10% 30% 70%

HBPU-1 260 310 380 358 15.50 20.19

HBPU-2 235 290 360 324 14.80 17.98
HBPU-3 230 280 355 351 14.30 15.14
3%oMMT + HBPU-1 280 330 400 370 16.31 26.29
3%oMMT + HBPU-2 245 300 385 344 15.25 24.19
3%oMMT + HBPU-3 240 300 375 361 14.90 23.14

Fig. 4. Tensile strength and elongation of hyperbranched polyurethane systems.

Fig. 5. Coating properties of hyperbranched polyurethane systems.

Fig. 6. Scratch hardness and impact resistance of hyperbranched polyurethane systems.

 R.H. Patel, K.S. Patel / Progress in Organic Coatings 88 (2015) 283–292 287

Fig. 7. FTIR spectra of (a) neat hyperbranched polyurethane systems. FTIR spectra of (b) hyperbranched polyurethane composite systems.
288 R.H. Patel, K.S. Patel / Progress in Organic Coatings 88 (2015) 283–292

Fig. 8. (a) 1 H NMR spectrum (b) 13 C NMR spectrum (c) 31 P NMR spectrum of the hyperbranched polyurethane based on TDI.

2.4. Preparation of organo-modified clay
The hyperbranched polyurethanes thus prepared were used for
the preparation of nano-composites and nano-coatings. To make
the clay compatible with hydrophobic polymer, modification of
clay was required. Modification of montmorillonite clay was done
according to the method reported in the literature [7]. In this
method 5 g of Na-MMT clay was dispersed at room temperature in
500 ml distilled water under continuous stirring of 24 h. An aqueous
solution of hexadecyl tri-methyl ammonium bromide (equivalent
to the cation exchange capacity of MMT-clay) was added into the
above dispersed solution. The resultant mixture was kept under
stirring for 12 h. The modified organo clay was filtered through
Whatman filter paper and washed several times with distilled
water. After drying, the organo-modified clay (o-MMT) was ground
properly to obtain fine powder of particle size less than 100 ␮m.
2.5. Characterization of nano-clay
The XRD analysis was performed using a Phillips Model Xpert
MPD (Holland) diffractometer with Cu K␣ radiation. The XRD pat-
tern of modified and unmodified clays is given in Fig. 2. The
d-spacing of unmodified montmorillonite clay and organomodified
clay are 14.64 Å (2 = 6.0361) and 17.82 Å (2 = 4.9601) respectively.
This shows an increase in interlayer distance of pristine clay from
14.64 Å to 17.82 Å for o-MMT. This increase in d-spacing may be due
 R.H. Patel, K.S. Patel / Progress in Organic Coatings 88 (2015) 283–292
Fig. 9. (a) Thermograms of neat hyperbranched polyurethane systems. (b) Thermograms of hyperbranched nano-clay composite systems with 3 wt% OMMT.
to the intercalation of alkyl ammonium group in the galleries by
replacing Na+ cation. The Average particle size of o-MMT clay was
38.60 nm as calculated from XRD pattern with interlayer distance
of 3.18 Å [8].
2.6. Characterization of flame retardant hyperbranched
polyurethanes
FT-IR study of flame retardant hyperbranched polyurethanes
was carried out with Perkin Elmer USA (Model Spectrum GX, FT-IR)
spectrophotometer, in the wave number range of 400–4000 cm−1 .
The structure of HBPU-1 was confirmed [9,10] by taking 1 H
NMR and 13 C NMR spectra in 400 MHz NMR spectrometer using
d6 -DMSO (dimethyl siloxane) as the solvent and TMS (tetra methyl
silane) as an internal standard. 31 P NMR spectrum was also taken
with the same spectrophotometer with 85% phosphoric acid as
internal standard. The spectra are given in Fig. 8.
Number average molecular weight and weight average molec-
ular weight were determined by gel permeation chromatographic
289
technique (GPC) using THF (tetra hydrofuran) as mobile phase with
the flow rate of 1 ml per second using polystyrene as standard in
Perkin Elmer USA (Model Series 200). Data are shown in Table 1.
Elemental analysis for carbon and hydrogen was carried out in
Perkin Elmer USA (Model 2400 series II) and these values are in good
agreement with the calculated values. These data are also given in
Table 1.
2.7. Preparation of flame retardant hyperbranched polyurethane
nano-clay composites and nano-clay coatings
Formulations to prepare nano-clay composites and coatings,
following method was used. Required amount of polyurethane
(HBPU) was mixed with xylene/MEK solvent mixture (1:4) with
constant stirring. The o-MMT clay was added into the above solu-
tion with vigorous stirring for 2 h at 50–55 ◦ C temperature to
disperse in HBPU resin. The mixture was degassed under vacuum
for few minutes [8]. Thus numbers of formulations were prepared
290 R.H. Patel, K.S. Patel / Progress in Organic Coatings 88 (2015) 283–292
Fig. 10. (a) Neat HBPU system (b) 3 wt% HBPU system (c) 5 wt% HBPU system.
using different types of HBPUs and different concentration (1%, 3%
and 5% Wt./Wt. of HBPU resin) of o-MMT clay.
To prepare nano-clay composites, the formulations (Fig. 3)
were poured one by one into the preheated Teflon mold of size
0.2 cm × 5 cm × 9 cm. The mold was placed on a triangular leveling
plate and leveled by moving the rotating screw of the plate. The
curing time of the formulations was 8 h at room temperature and
post curing was carried out at 120 ◦ C for 4 h. After cooling the mold
to room temperature, the composite films were removed from the
mold and used for the evaluation of various properties. Fig. 4 shows
the types of nano-clay composites and their properties.
Same formulations were used for making nano-clay coatings.
Mild steel panels were cleaned properly and the formulations were
coated on the panels with the help of film applicator. Moisture cur-
ing process was used for the curing by keeping the panels at room
temperature. After 8 h the panels were post cured for 4 h at 120 ◦ C.
To compare the properties of nano-clay composites and
coatings, films and coating panels of the neat HBPUs have also been
prepared using the above methods.
2.8. Characterization of neat polyurethane – nano clay
composites and coatings
Thermogravimetric analysis was performed on TGA-PYRIS 7,
USA thermal analyzer. Cured sample (neat HBPUs and nano-clay
composites using 3 wt% clay), about 8–10 mg was placed in the
sample pan and heated from 50 to 600 ◦ C under air atmosphere
(60 ml/min) at a heating rate of 10 ◦ C/min. The weight loss was
recorded as a function of temperature, and reported in Table 2.
Flame retardancy of the films were tested by limiting oxy-
gen index (LOI) analysis (ASTM D 2863) and vertical burning test
method UL-94 (ASTM D 3801). The size of the sample of LOI an
UL-94 are 10 cm × 50 cm and 1.5 mm thickness & 20 cm × 5 cm
respectively as per ASTM standards. LOI is the measurement of
minimum concentration of oxygen in terms of volume percent, in
a mixture of oxygen and nitrogen, that will just support flaming
combustion of a material under specified conditions [11].
In UL-94 test method, sample achieves V0 rating when it must
self-extinguished within 10 s and at the same time there is no sign
of dripping the burning polymer, while if the sample continuously
burns or if drips the polymer, V1 or V2 rating is assigned [12].
Mechanical properties of films like tensile and elongation at
break were measured for neat film and nano-clay composites and
data are shown in Fig. 4.
The morphological study was done with the help of scanning
electron micrograph of HBPU and their composite.
To obtain reproducible coating physical properties like, pot life,
surface drying, tack free drying and hard drying was measured with
respect to room temperature and time (ASTM D 1338). All these
data for various hyperbranched polyurethanes and their nano-clay
coatings are given in Fig. 5.
Mechanical properties used for the testing of coatings (Fig. 6)
are scratch hardness (ASTM D 5178) and tabular impact test (ASTM
D 2794).
3. Results and discussion
3.1. FTIR analysis
FTIR analysis was performed to determine the functional groups
of polymers (Fig. 7) shows the infrared spectra of the neat hyper-
branched polyurethanes and their nano-clay composites. In neat
HBPUs (Fig. 7a) stretching frequency for OH functional group is
observed at 3350 cm−1 [13]. The peaks at 1598 and 1460 cm−1
is due to the stretching frequency of C C in the aliphatic chain
and aromatic ring respectively. The spectra shows band around
2164 cm−1 for NCO group. The bands appearing at 1168 cm−1 and
1039 cm−1 correspond to P O stretching frequency and P O C
stretching frequency respectively [14].
In HBPU nano-clay composites (Fig. 7b) broad band at 3029 cm−1
is due to the N H stretching vibration of urethane moiety. The
peak at 1736 cm−1 is due to C O group of urethane and at
1413–1452 cm−1 is due to the C C stretching of aromatic ben-
zene rings. The peak at 838 cm−1 is due to the p-substituted
benzene ring of the polymer moiety. In case of nano-composites,
the peaks due to OH and NCO groups are absent. This
proves that the cross-linking occur through the terminal OH
and NCO group of hyperbranched polyurethanes. Besides these
 R.H. Patel, K.S. Patel / Progress in Organic Coatings 88 (2015) 283–292
Fig. 11. LOI data of hyperbranched system and their composites.
peaks nano-composites also contain the characteristic bands of
montmorillonite at 1193 cm−1 , 968 cm−1 , 557 cm−1 and 463 cm−1
respectively for the stretching vibrations of Si O Si, Al O Si,
Al Si and Si O bending vibration of montmorillonite [8]. The pres-
ence of these bands indicates the successful incorporation of the
HBPU into the layered silicate framework of nano-clay composites
[15].
3.2. NMR analysis
The structure of HBPU was characterized by a combination of
1 H-, 13 C- and 31 P NMR spectroscopy. The 1 H NMR spectrum (Fig. 8a)
of HBPU-1 is divided into two parts [16,17]. The first part describes
the spectrum of castor oil in polymer backbone chain. The aliphatic
chains of castor oil give the signals at ı 1.3 ppm for CH2 protons
and at ı 0.90 ppm for the protons of terminal CH3 group. The sig-
nal at ı 1.92 ppm is for the CH2 protons attached to C C in the
aliphatic chain.
The second part explains the branched structure of
polyurethane present on the castor oil backbone. The signal
at ı 5.5 ppm for the proton of (C O)NH linkage and the signal
at ı 6.90 ppm is for the proton of aromatic phenol (Ar OH). The
sharp singlet at ı 3.3 ppm is for CH3 groups of bisphenol-A
in triol moiety and at ı 2.5 ppm is for CH3 proton of toluene
diisocyanate.
The 13 C NMR spectrum (Fig. 8b) shows the peak at ı 69 ppm
for disubstituted ethylene O (CH2 CH2 ) O moiety present in
polyurethane branch. The signals at ı 143 ppm and ı 137 ppm
correspond to C O P and C O H respectively. The peaks at ı
128 ppm and ı 134 ppm assigned to phenoxy carbons ( O C6 H5 ).
Peaks around ı 15.5 to 20.8 ppm and ı 28.1 to 28.5 ppm represent
the carbon atoms of long chain fatty acid in triglyceride (castor oil).
The 31 P NMR spectrum (Fig. 8c) shows a peak at −16 ppm
confirms the presence of phosphorus moiety of the triphenyl phos-
phate.
3.3. Thermogravimetric analysis
Thermal stability of polyurethanes depends on the types of the
elements present in the chain, the urethane linkage and the aro-
maticity of the polymer chain. The thermograms of the systems
are shown in Fig. 9. The degradation of polyurethane occurs mainly
291
due to the depolymerization process in polyurethanes [18]. The
bonds between the polyols and urethane linkages start to degrade
around 230–260 ◦ C temperature. The bonds with the phosphorous
are thermally more liable and start to decompose fast produc-
ing a layer of char on the product surface and thus impart flame
retardancy. Analysis of the data in Table 2 reveals that HBPU-1 hav-
ing rigid aromatic toluene moiety in the chain structure possesses
highest thermal stability. Due to the presence of flexible hexam-
ethylene groups, lowest stability is observed in HBPU-3 while the
IPDI based HBPU-2 having both the aliphatic methylene and cyclo
aliphatic ring structure shows stability in-between the above two
systems.
The percentage weight loss for 10%, 30% and 70% and the char
values of neat polyurethanes and their nano-clay composites are
shown in Table 2. The integral procedure decomposition temper-
ature (IPDT) calculated from the respective thermograms using
Doyle’s method and the value of activation energy calculated by
Broido’s method are also given in this table. The activation energy
of IPDI based system falls between the most stable TDI based system
and least stable HMDI based system.
Incorporation of clay increases the thermal stability only in
the range of 10–20 ◦ C. In these cases also the thermal stability
cannot be improved much due to the low temperature stability
and flame retardant characteristics of phosphorous moiety of the
polyurethanes.
3.4. Morphology study
The micro structure study was carried out using scanning elec-
tron microscope. The surface morphology of the neat film of TDI
based hyperbranched polyurethane in Fig. 10(a) appears as very
homogeneous and on addition of nano-clay, particles start to
disperse into the polyurethane and with the addition of 3 wt% nano-
clay dispersion occurs to a certain level as shown in Fig. 10(b), while
in case of 5 wt% loading of clay particles aggregate which can be
adjudged from Fig. 10(c).
3.5. Flame retardant properties of films
The flame retardant properties of nano-clay composites and
neat polymers tested by Limiting of oxygen index (LOI) and ver-
tical burning test (UL-94) are shown in Fig. 11. These properties of
292 R.H. Patel, K.S. Patel / Progress in Organic Coatings 88 (2015) 283–292
neat polyurethanes and their nano-clay composites are compara-
ble with their thermal decomposition data. Nano-clay composites
have higher LOI and char values compare to the neat polymers. It
has seen that the presence of nano-clay does not make any signifi-
cant change in the LOI value of nano-clay composites [19]. Because
of the higher aromaticity of TDI based systems, flame retardancy is
higher compare to the IPDI and HMDI based systems. The results
are also supported by their UL-94 test data, where all the systems
show V0 rating.
Tensile properties of composite films are also given in Fig. 4.
Nano-clay composites containing 3 wt% nano-clay gives maximum
tensile strength compare to the other systems. HMDI based systems
show highest elongation compare to the other systems because of
the present of flexible methylene chain moiety.
3.6. Mechanical properties of coatings
The mechanical properties of the neat polyurethanes and their
nano-clay coatings are shown in Fig. 6. In the neat HBPUs, TDI
based systems have highest scratch hardness and impact resis-
tance compare to the other two HBPUs. It has observed that the
clay content have remarkable effect on the mechanical properties
of coatings. Both the scratch hardness and impact resistance of the
nano-clay coatings are higher compare to the neat polyurethanes.
The highest value of mechanical properties are observed with
3 wt% nano-clay content. Other properties like pencil hardness,
flexibility and adhesion (cross-hatch) are inferior with 5 wt% nano-
clay. Proper dispersion of clay with polymer occurs up to 3 wt%
nano-clay content while above this amount clay particles start to
aggregate resulting in poor mechanical properties. Due to their
hyperbranched structure polyurethanes possess large number of
end groups, providing many crosslinking sites. Therefore coating
properties of neat hyperbranched polyurethanes are nearly two
times higher compare to the linear polyurethanes, which is pub-
lished elsewhere [13].
4. Conclusions
Aiming at the production of low flammability and superior prop-
erties, an aromatic phosphorous based polyol was allowed to react
with two different types of aliphatic polyols (linear and non-linear)
to produce flame retardant hyperbranched polyurethanes using
A2 + B3 route.
HBPUs were used for the preparation of nano-composites and
nano-coatings. Measurements of mechanical properties of com-
posites showed around 10–12% improvement in tensile properties
but the coatings showed an increase of 50% scratch hardness prop-
erty for the hyperbranched polyurethanes compared to the linear
polyurethanes [13] due to the availability of higher cross-linking
sites in hyperbranched polyurethanes.
Addition of organo-modified clay caused an improvement in
the mechanical properties which usually occurs in the presence
of 3 wt% clay.
Acknowledgements
The financial assistance from UGC and CSIR, New Delhi, India is
gratefully acknowledged. Appreciation is also expressed to Sophis-
ticated Instrumentation Center for Applied Research and Testing
(SICART), Charutar Vidya Mandal, Vallabh Vidyanagar, and Reliable
Paints Industries, GIDC, Vadodara for the analysis and testing of the
samples.
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