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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.
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. 2. XRD images of (a) unmodified MMT clay (b) modified MMT clay. 2.3.2. Step-II
The solid triol (TBAMP) was dissolved in xylene/MEK mixture
2.2. Synthesis of phosphorous containing triol (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
The phosphorous containing triol, tris (bisphenol-A) mono (step-I) with continuous stirring at 10 ◦ C temperature for 1 h. After
phosphate (TBAMP) was synthesized by reacting bisphenol-A the completion of addition, the reaction was heated at 60 ◦ C for 2 h.
(3 mol) and phosphorous oxychloride (1 mol) in presence of a Reaction conditions were controlled strictly to prevent the gelation
catalyst N,N-dimethyl aniline (0.01%) according to the reported of the product during the reaction. The excess solvent was removed
method [6]. This triol was used to react with polyurethane- from the end product by vacuum distillation to get a flame retardant
pre-polymer (step-I) to prepare hyperbranched polyurethanes hyperbranched polyurethane (HBPU-1).
(step-II). Other two flame retardant hyperbranched polyurethanes
2.3. Synthesis of hyperbranched polyurethanes HBPU-2 and HBPU-3 were prepared by reacting two different diiso-
cyanates, IPDI and HMDI respectively with triol using the above
2.3.1. Step-I method. Fig. 1 shows the reaction steps involved in the synthesis
Castor oil (1.0 mol) and polyethylene glycol (1.0 mol) and 50 ml of HBPUs. The physical properties of the polyurethanes are given
solvent mixture of xylene/methyl ethyl ketone (1:4) were taken in 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
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 (%)
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 Whatman filter paper and washed several times with distilled
water. After drying, the organo-modified clay (o-MMT) was ground
The hyperbranched polyurethanes thus prepared were used for properly to obtain fine powder of particle size less than 100 m.
the preparation of nano-composites and nano-coatings. To make
the clay compatible with hydrophobic polymer, modification of 2.5. Characterization of nano-clay
clay was required. Modification of montmorillonite clay was done
according to the method reported in the literature [7]. In this The XRD analysis was performed using a Phillips Model Xpert
method 5 g of Na-MMT clay was dispersed at room temperature in MPD (Holland) diffractometer with Cu K␣ radiation. The XRD pat-
500 ml distilled water under continuous stirring of 24 h. An aqueous tern of modified and unmodified clays is given in Fig. 2. The
solution of hexadecyl tri-methyl ammonium bromide (equivalent d-spacing of unmodified montmorillonite clay and organomodified
to the cation exchange capacity of MMT-clay) was added into the clay are 14.64 Å (2 = 6.0361) and 17.82 Å (2 = 4.9601) respectively.
above dispersed solution. The resultant mixture was kept under This shows an increase in interlayer distance of pristine clay from
stirring for 12 h. The modified organo clay was filtered through 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) 283–292 289
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 technique (GPC) using THF (tetra hydrofuran) as mobile phase with
replacing Na+ cation. The Average particle size of o-MMT clay was the flow rate of 1 ml per second using polystyrene as standard in
38.60 nm as calculated from XRD pattern with interlayer distance Perkin Elmer USA (Model Series 200). Data are shown in Table 1.
of 3.18 Å [8]. 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
2.6. Characterization of flame retardant hyperbranched Table 1.
polyurethanes
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% of dripping the burning polymer, while if the sample continuously
and 5% Wt./Wt. of HBPU resin) of o-MMT clay. burns or if drips the polymer, V1 or V2 rating is assigned [12].
To prepare nano-clay composites, the formulations (Fig. 3) Mechanical properties of films like tensile and elongation at
were poured one by one into the preheated Teflon mold of size break were measured for neat film and nano-clay composites and
0.2 cm × 5 cm × 9 cm. The mold was placed on a triangular leveling data are shown in Fig. 4.
plate and leveled by moving the rotating screw of the plate. The The morphological study was done with the help of scanning
curing time of the formulations was 8 h at room temperature and electron micrograph of HBPU and their composite.
post curing was carried out at 120 ◦ C for 4 h. After cooling the mold To obtain reproducible coating physical properties like, pot life,
to room temperature, the composite films were removed from the surface drying, tack free drying and hard drying was measured with
mold and used for the evaluation of various properties. Fig. 4 shows respect to room temperature and time (ASTM D 1338). All these
the types of nano-clay composites and their properties. data for various hyperbranched polyurethanes and their nano-clay
Same formulations were used for making nano-clay coatings. coatings are given in Fig. 5.
Mild steel panels were cleaned properly and the formulations were Mechanical properties used for the testing of coatings (Fig. 6)
coated on the panels with the help of film applicator. Moisture cur- are scratch hardness (ASTM D 5178) and tabular impact test (ASTM
ing process was used for the curing by keeping the panels at room D 2794).
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 3. Results and discussion
prepared using the above methods.
3.1. FTIR analysis
2.8. Characterization of neat polyurethane – nano clay FTIR analysis was performed to determine the functional groups
composites and coatings of polymers (Fig. 7) shows the infrared spectra of the neat hyper-
branched polyurethanes and their nano-clay composites. In neat
Thermogravimetric analysis was performed on TGA-PYRIS 7, HBPUs (Fig. 7a) stretching frequency for OH functional group is
USA thermal analyzer. Cured sample (neat HBPUs and nano-clay observed at 3350 cm−1 [13]. The peaks at 1598 and 1460 cm−1
composites using 3 wt% clay), about 8–10 mg was placed in the is due to the stretching frequency of C C in the aliphatic chain
sample pan and heated from 50 to 600 ◦ C under air atmosphere and aromatic ring respectively. The spectra shows band around
(60 ml/min) at a heating rate of 10 ◦ C/min. The weight loss was 2164 cm−1 for NCO group. The bands appearing at 1168 cm−1 and
recorded as a function of temperature, and reported in Table 2. 1039 cm−1 correspond to P O stretching frequency and P O C
Flame retardancy of the films were tested by limiting oxy- stretching frequency respectively [14].
gen index (LOI) analysis (ASTM D 2863) and vertical burning test In HBPU nano-clay composites (Fig. 7b) broad band at 3029 cm−1
method UL-94 (ASTM D 3801). The size of the sample of LOI an is due to the N H stretching vibration of urethane moiety. The
UL-94 are 10 cm × 50 cm and 1.5 mm thickness & 20 cm × 5 cm peak at 1736 cm−1 is due to C O group of urethane and at
respectively as per ASTM standards. LOI is the measurement of 1413–1452 cm−1 is due to the C C stretching of aromatic ben-
minimum concentration of oxygen in terms of volume percent, in zene rings. The peak at 838 cm−1 is due to the p-substituted
a mixture of oxygen and nitrogen, that will just support flaming benzene ring of the polymer moiety. In case of nano-composites,
combustion of a material under specified conditions [11]. the peaks due to OH and NCO groups are absent. This
In UL-94 test method, sample achieves V0 rating when it must proves that the cross-linking occur through the terminal OH
self-extinguished within 10 s and at the same time there is no sign and NCO group of hyperbranched polyurethanes. Besides these
R.H. Patel, K.S. Patel / Progress in Organic Coatings 88 (2015) 283–292 291
peaks nano-composites also contain the characteristic bands of due to the depolymerization process in polyurethanes [18]. The
montmorillonite at 1193 cm−1 , 968 cm−1 , 557 cm−1 and 463 cm−1 bonds between the polyols and urethane linkages start to degrade
respectively for the stretching vibrations of Si O Si, Al O Si, around 230–260 ◦ C temperature. The bonds with the phosphorous
Al Si and Si O bending vibration of montmorillonite [8]. The pres- are thermally more liable and start to decompose fast produc-
ence of these bands indicates the successful incorporation of the ing a layer of char on the product surface and thus impart flame
HBPU into the layered silicate framework of nano-clay composites retardancy. Analysis of the data in Table 2 reveals that HBPU-1 hav-
[15]. ing rigid aromatic toluene moiety in the chain structure possesses
highest thermal stability. Due to the presence of flexible hexam-
3.2. NMR analysis ethylene groups, lowest stability is observed in HBPU-3 while the
IPDI based HBPU-2 having both the aliphatic methylene and cyclo
The structure of HBPU was characterized by a combination of aliphatic ring structure shows stability in-between the above two
1 H-, 13 C- and 31 P NMR spectroscopy. The 1 H NMR spectrum (Fig. 8a) systems.
of HBPU-1 is divided into two parts [16,17]. The first part describes The percentage weight loss for 10%, 30% and 70% and the char
the spectrum of castor oil in polymer backbone chain. The aliphatic values of neat polyurethanes and their nano-clay composites are
chains of castor oil give the signals at ı 1.3 ppm for CH2 protons shown in Table 2. The integral procedure decomposition temper-
and at ı 0.90 ppm for the protons of terminal CH3 group. The sig- ature (IPDT) calculated from the respective thermograms using
nal at ı 1.92 ppm is for the CH2 protons attached to C C in the Doyle’s method and the value of activation energy calculated by
aliphatic chain. Broido’s method are also given in this table. The activation energy
The second part explains the branched structure of of IPDI based system falls between the most stable TDI based system
polyurethane present on the castor oil backbone. The signal and least stable HMDI based system.
at ı 5.5 ppm for the proton of (C O)NH linkage and the signal Incorporation of clay increases the thermal stability only in
at ı 6.90 ppm is for the proton of aromatic phenol (Ar OH). The the range of 10–20 ◦ C. In these cases also the thermal stability
sharp singlet at ı 3.3 ppm is for CH3 groups of bisphenol-A cannot be improved much due to the low temperature stability
in triol moiety and at ı 2.5 ppm is for CH3 proton of toluene and flame retardant characteristics of phosphorous moiety of the
diisocyanate. polyurethanes.
The 13 C NMR spectrum (Fig. 8b) shows the peak at ı 69 ppm
for disubstituted ethylene O (CH2 CH2 ) O moiety present in 3.4. Morphology study
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 The micro structure study was carried out using scanning elec-
128 ppm and ı 134 ppm assigned to phenoxy carbons ( O C6 H5 ). tron microscope. The surface morphology of the neat film of TDI
Peaks around ı 15.5 to 20.8 ppm and ı 28.1 to 28.5 ppm represent based hyperbranched polyurethane in Fig. 10(a) appears as very
the carbon atoms of long chain fatty acid in triglyceride (castor oil). homogeneous and on addition of nano-clay, particles start to
The 31 P NMR spectrum (Fig. 8c) shows a peak at −16 ppm disperse into the polyurethane and with the addition of 3 wt% nano-
confirms the presence of phosphorus moiety of the triphenyl phos- clay dispersion occurs to a certain level as shown in Fig. 10(b), while
phate. in case of 5 wt% loading of clay particles aggregate which can be
adjudged from Fig. 10(c).
3.3. Thermogravimetric analysis
3.5. Flame retardant properties of films
Thermal stability of polyurethanes depends on the types of the
elements present in the chain, the urethane linkage and the aro- The flame retardant properties of nano-clay composites and
maticity of the polymer chain. The thermograms of the systems neat polymers tested by Limiting of oxygen index (LOI) and ver-
are shown in Fig. 9. The degradation of polyurethane occurs mainly 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- HBPUs were used for the preparation of nano-composites and
ble with their thermal decomposition data. Nano-clay composites nano-coatings. Measurements of mechanical properties of com-
have higher LOI and char values compare to the neat polymers. It posites showed around 10–12% improvement in tensile properties
has seen that the presence of nano-clay does not make any signifi- but the coatings showed an increase of 50% scratch hardness prop-
cant change in the LOI value of nano-clay composites [19]. Because erty for the hyperbranched polyurethanes compared to the linear
of the higher aromaticity of TDI based systems, flame retardancy is polyurethanes [13] due to the availability of higher cross-linking
higher compare to the IPDI and HMDI based systems. The results sites in hyperbranched polyurethanes.
are also supported by their UL-94 test data, where all the systems Addition of organo-modified clay caused an improvement in
show V0 rating. the mechanical properties which usually occurs in the presence
Tensile properties of composite films are also given in Fig. 4. of 3 wt% clay.
Nano-clay composites containing 3 wt% nano-clay gives maximum
tensile strength compare to the other systems. HMDI based systems Acknowledgements
show highest elongation compare to the other systems because of
the present of flexible methylene chain moiety. The financial assistance from UGC and CSIR, New Delhi, India is
gratefully acknowledged. Appreciation is also expressed to Sophis-
3.6. Mechanical properties of coatings ticated Instrumentation Center for Applied Research and Testing
(SICART), Charutar Vidya Mandal, Vallabh Vidyanagar, and Reliable
The mechanical properties of the neat polyurethanes and their Paints Industries, GIDC, Vadodara for the analysis and testing of the
nano-clay coatings are shown in Fig. 6. In the neat HBPUs, TDI samples.
based systems have highest scratch hardness and impact resis-
tance compare to the other two HBPUs. It has observed that the References
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