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Progress in Organic Coatings

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Hyperbranched polyurethane (HBPU)-urea and HBPU-imide coatings:

Effect of chain extender and NCO/OH ratio on their properties
Aswini K. Mishra a , Ramanuj Narayan a , K.V.S.N. Raju a,∗ , Tejraj M. Aminabhavi b
a
Organic Coatings and Polymers Division, Indian Institute of Chemical Technology, Hyderabad 500 607, India
b
CSIR Emeritus Scientist, Sonia Education Trust’s College of Pharmacy, Dharwad 580 002, India

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

Article history: Effect of chain extender and NCO/OH ratio on the properties of hyperbranched polyurethane (HBPU)-
Received 31 May 2011 urea and HBPU-imide coatings were examined. The NCO terminated pre-polymers were prepared by
Received in revised form 31 October 2011 reacting the first (G1) and the second (G2) generation hyperbranched polyester polyols (HBP-G1 and
Accepted 29 November 2011
HBP-G2) with excess diisocyanate. The excess NCO content of the prepolymer was reacted with differ-
Available online xxx
ent chain extenders viz., 3-aminopropyl triethoxysilane (APTES), pyromellitic dianhydride (PMDA) and
N-hydroxyphthalimide (NHTM) to obtain HBPU-urea or HBPU-imide coatings. The structure–property
Keywords:
relationships of the different coatings were investigated by FTIR peak deconvolution, and these data
Hyperbranched polyester
Polyurethane coatings
suggests the highest extent of hydrogen bonding interaction for PMDA-based coatings, which increases
FTIR with increasing NCO/OH ratio. Film properties were evaluated by TGA, DMTA, UTM and contact angle
DMTA measurements; these results were supported by FTIR deconvolution results. As per contact angle mea-
surements, hydrophobicity of coatings increased by increasing NCO/OH ratio. The adhesive strength,
abrasion resistance, alkali resistance, and gel content of the coatings were also evaluated.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction suggesting the use of HBPs as an alternative to branched architec-

Polyurethane (PU) coatings are becoming increasingly impor-
tant in view of their excellent mechanical properties, good hardness
and high abrasion resistance [1]. These properties result from
a combination of chain segment flexibility, rigidity of aromatic
units, chain entanglement and orientation of hard-soft segments.
However, poor heat resistance and mechanical deformation at
higher temperature (>80 ◦ C) of the conventional PU coatings
limit their high temperature applications [2]. For PU to be use-
ful at high temperatures, its architecture should be modified by
introducing thermally stable heterocyclic imide rings or siloxane
linkages [3,4]. Many attempts have been made in the literature to
incorporate imide rings into PU backbone through chemical mod-
ifications [5–13]. However, recent efforts [14–19] on modifying
the architecture of PU have led to novel tailor-made functional
PUs using dendrimers or hyperbranched polymers (HBPs). The
synthesis of dendrimer is quite tedious and requires several protec-
tion/deprotection steps as well as extensive purifications between
successive generations. Because of their low yield and high cost,
dendrimers have limited industrial applications compared to HBPs,
∗ Corresponding author. Tel.: +91 40 27193208; fax: +91 40 27193991.
E-mail addresses: kvsnraju@iict.res.in, drkvsnraju@gmail.com (K.V.S.N. Raju).
tures due to their cost-effectiveness.
Various types of HBPs developed earlier are based on
polyphenylene [20], poly(ether ketone) [21,22], poly(4-
chloromethylstyrene) [23], polycarbonate [24], polyesters [25],
polyamides [26,27], and polyurethanes [28,29]; their properties
are almost similar to dendrimers [30–32]. Physical and thermal
properties of PUs have been altered by changing the compositions
and hard/soft segment ratios [33–35]. Barikani and Hepburn [36]
examined the effects of structures of different types of chain
extenders and diisocyanates on the thermal stability of PUs based
on polycaprolactone diol. Minoura et al. [35,37] investigated
the properties of different types of PUs derived from various
diols and diisocyanates. These results confirmed that mechan-
ical properties are related to crosslink density, concentration
of polar groups, crystallinity, etc. Earlier, we have examined
[38–41] the effect of chain extender on thermo-mechanical and
surface properties of different PU-urea-imide and PU-imide/o-clay
hybrid coatings by carrying out reactions on linear polymeric
architecture.
Realizing not much work reported on the effect of chain exten-
ders, type of diisocyanate, soft and hard segments and NCO/OH
ratios on thermo-mechanical and coating characteristics of HBPs, in
this study, we have undertaken a comprehensive study on the effect
of chain extender type and NCO/OH ratio on the properties of differ-
ent HBPU-urea and HBPU-imide coatings. The structure–property

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doi:10.1016/j.porgcoat.2011.11.027

Please cite this article in press as: A.K. Mishra, et al., Hyperbranched polyurethane (HBPU)-urea and HBPU-imide coatings: Effect of chain extender
and NCO/OH ratio on their properties, Prog. Org. Coat. (2011), doi:10.1016/j.porgcoat.2011.11.027
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Fig. 1. The structures of different chain extenders used in the synthesis of HBPU-
urea and HBPU-imide coatings.
relationships of different coating systems were evaluated by FTIR
peak deconvolution. The deconvolution result supports to the
DMTA, TGA, UTM and contact angle data.
2. Experimental
2.1. Materials
Isophrone diisocyanate (IPDI), 4,4 -bis-methylene cyclohex-
ane diisocyanate (HMDI), bis(hydroxymethyl) propionic acid
(bis-MPA), 3-aminopropyl triethoxysilane (APTES) and dibutyltin
dilaurate (DBTL) were procured from Aldrich (Milwaukee, WI);
NHTM, PMDA, dimethyl formamide (DMF) and p-toluene sulfonic
acid (p-TSA), were obtained from s.d. fine chemicals (Mumbai,
India); triethanol amine (TEA) and methyl isobutyl ketone (MIBK)
were purchased from Ranbaxy (Mumbai, India). All the solvents
were used as received and freed from moisture by adding 4◦ A
molecular sieves before use.
2.2. Synthesis of HBPU-urea and HBPU-imide coating films
The NCO-terminated prepolymer resin was prepared by car-
rying out the reaction in a 100 mL three necked round bottom
flask equipped with a thermometer, dropping funnel and by con-
tinuously purging with nitrogen flow. The reaction was carried
out over a digital magnetic heating/stirrer instrument. Initially,
a fixed weight of hyperbranched polyester polyol (HBP-G1 or
HBP-G2) was dissolved in polar aprotic solvents by heating. This
diluted polyester was added drop-wise through a dropping fun-
nel to the flask containing HMDI at different NCO/OH eq. ratios at
60 ◦ C and the addition was continued for 15–20 min. After com-
plete addition, the urethanification reaction was carried out for
another 3 h at 70 ◦ C in the presence of 0.5 wt.% of DBTL as a
catalyst.
In the next step, the synthesized NCO terminated prepolymer
resin was divided into three equal parts and the extra NCO con-
tent was calculated by standard dibutylamine titration method.
This extra NCO content of each part was completely chain extended
with APTES, NHTM and PMDA to get either the HBPU-urea or HBPU-
imide coatings respectively. The coating films were obtained by
casting different chain extender containing prepolymer resins on
a tin foil supported over a glass plate through a manual driven
square applicator. The APTES and NHTM chain extender based pre-
polymer resins were cured at laboratory humidity condition for
about 20–25 days in the presence of DBTL catalyst and tagostab
as surfactant [42]. While, the PMDA chain extender based coating
was thermal cured in an air circulated oven at 100 ◦ C for 20 min
and at 120 ◦ C for 10 min. The imidization reaction in the later case
occurs through the formation of a five member cyclic transition
state [38].
The supported films were extracted after amalgamation and
cleaning. The absence of free NCO peak at 2270 cm−1 in the FTIR
spectrum of various HBPU-urea and HBPU-imide coatings after
curing confirms the completion of chain extension reaction. The
sample codes, chemical composition and equivalent ratios used
for the synthesis of various chain extender based HBPU-urea or
HBPU-imide coatings are given in Table 1. Whereas, the detailed
reaction condition along with the chain extenders used are shown
in Schemes 1 and 2, and Fig. 1, respectively.
Please cite this article in press as: A.K. Mishra, et al., Hyperbranched polyurethane (HBPU)-urea and HBPU-imide coatings: Effect of chain extender
and NCO/OH ratio on their properties, Prog. Org. Coat. (2011), doi:10.1016/j.porgcoat.2011.11.027
2.3. Characterization methods
FTIR spectra (Thermo Nicolet Nexus 670 spectrometer, USA) of
different cured samples were obtained by taking the diluted solu-
tions of different chain extender based prepolymer resins over
dry KBr disc. The discs were completely cured to get different
HBPU-urea or HBPU-imide coatings and used for FTIR analysis. Each
sample was scanned 68 times with a resolution setting of 4 cm−1
and spectra were determined over the range of 400–4000 cm−1 .
Viscoelastic behavior of the films (15 mm × 10 mm × 0.15 mm)
in the temperature range of 30–200 ◦ C was analyzed with DMTA
instrument (DMTA-IV, Rheometric Scientific Inc., New Jersey, USA)
in a tensile mode at a frequency of 1 Hz and at the heating rate
of 3 ◦ C min−1 .Perkin Elmer TGA 7 instrument was used to study
thermal decomposition profile of different coatings at a constant
heating rate of 10 ◦ C min−1 in a nitrogen atmosphere from 30 ◦ C to
600 ◦ C. The sample weight of <10 mg was used for TGA analysis.
The adhesive strength of different coated samples on the mild
steel panel was determined by Pull-off test (Microtech Tensiome-
ter, UK). For this, the metal discs were pretreated with acid cleaning
(chemical pickling), washed with distilled water and acetone before
application of coating with a spin coater.
The abrasion resistance of the coatings was studied by Taber
abrasion resistance instrument. The tensile strength of different
coating films were evaluated with AGS-10kNG, SHIMADZU (Japan)
system connected with AUTOGRAPH controller/measurement unit.
For this the samples were cut into the dumbbell-shaped structure.
3. Results and discussion
3.1. FTIR analysis
Fig. 2 shows the representative FTIR spectra of different HBPU-
urea and HBPU-imide coatings in the range 400–4000 cm−1 . The
absence of free –NCO peak at 2270 cm−1 and appearance of dif-
ferent imide bands at 1780, 1730, 1380, 720 and 1078 cm−1
confirms the completion of curing reaction [43]. Presence of these
peaks also confirms the structure of HBPU-urea and HBPU-imide
coatings. However, the effect of variation of anhydride struc-
ture and NCO/OH ratios on hydrogen bonding ability of different
HBPU-imide and HBPU-urea coatings were evaluated by FTIR peak
deconvolution, wherein the baseline was corrected from 1600 to
1800 cm−1 for −C O zone and 3000–3800 cm−1 for –NH zone for
different HBPU-imide and HBPU-urea coatings. Fig. 3(a) and (b),
shows the representative deconvoluted −C O and −NH zones for
HBPU-imide coatings with the variation of anhydride structure.
The deconvoluted −C O zone (Fig. 3(a)), for the samples PU-G1-
1.2H-NHTM and PU-G1-1.2H-PMDA shows peak values at 1776,
1742, 1708 and 1648 cm−1 and were assigned to free imide, bonded
imide, free urethane and bonded urethane, respectively. Similarly,
the −NH zone deconvolution (Fig. 3(b)) for the above two samples
shows peak values at 3520, 3222 and 3120 cm−1 and were assigned
to free −NH, bonded −NH and overtone due to Fermi resonance,
respectively.
A comparative analysis of −C O and −NH zone decon-
volution study suggests more hydrogen bonded (NH· · ·O C−)
urethane/imide structures for PU-G1-1.4H-PMDA (observed from
hydrogen-bonded peak areas) than PU-G1-1.4H-NHTM. This result
is due to the more symmetrical and polar nature of PMDA struc-
ture than the NHTM chain extender structure. Fig. 3(c) and (d),
shows the representative deconvoluted −C O and −NH zones for
different HBPU-urea coatings with increasing the NCO/OH ratio.
The deconvoluted spectra of PU-G1-1.2H-APTES and PU-G1-1.4H-
APTES exhibit peak values at 1730, 1705, 1673, 1638 cm−1 due to
free urethane, bonded urethane, free urea and bonded urea in the
−C O zone and 3550, 3340, 3210 cm−1 due to free –NH, bonded
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Table 1
The chemical composition and sample codes used for the synthesis of different chain extender based HBPU-urea and HBPU-imide coatings.

Sample code for HBPU coatings Chemical composition of the Sample code Chemical composition NCO/OH ratios used for
polyester (mole ratios) for polyester of HBPU coating HBPU synthesis

PU-G1-1.2H-APTES TEA/bis-MPA (1:3) HBP-G1 HBP-G1/HMDI 1.2:1

PU-G1-1.2H-PMDA TEA/bis-MPA (1:3) HBP-G1/HMDI 1.2:1
PU-G1-1.4H-NHTM TEA/bis-MPA (1:3) HBP-G1/HMDI 1.4:1
PU-G1-1.4H-APTES TEA/bis-MPA (1:3) HBP-G1/HMDI 1.4:1
PU-G1-1.4H-PMDA TEA/bis-MPA (1:3) HBP-G1/HMDI 1.4:1
PU-G2-1.2H-NHTM TEA/bis-MPA (1:9) HBP-G2 HBP-G2/HMDI 1.2:1
PU-G2-1.2H-APTES TEA/bis-MPA (1:9) HBP-G2/HMDI 1.2:1
PU-G2-1.2H-PMDA TEA/bis-MPA (1:9) HBP-G2/HMDI 1.2:1
PU-G2-1.4H-NHTM TEA/bis-MPA (1:9) HBP-G2/HMDI 1.4:1
PU-G2-1.4H-APTES TEA/bis-MPA (1:9) HBP-G2/HMDI 1.4:1
PU-G2-1.4H-PMDA TEA/bis-MPA (1:9) HBP-G2/HMDI 1.4:1

−NH and overtone due to Fermi resonance in the −NH zone, respec-
tively [44]. The comparative deconvoluted peak area analysis of
the above two representative samples suggests more hydrogen
bonded structures for PU-G1-1.4H-APTES than PU-G1-1.2H-APTES.
This result is might be due to the presence of more number of
hard urethane/urea segments in the polymer matrix with increas-
ing NCO/OH ratio. The higher the content of hard segments, the
more is the inter/intra molecular hydrogen bonding interactions,
hence broader is the deconvoluted peak area [45].
3.2. Thermal property study
Thermal stability data of representative HBPU-urea and HBPU-
imide coatings are shown in Fig. 4(a) and (b), while the results
are summarized in Table 2. All the thermograms show a three-
step degradation profile in which the second step is prominent,
which starts above 260 ◦ C. The first step decomposition temper-
ature corresponds to urethane/urea bonds breaking, while the
second step is due to the decomposition of polyol soft segments
[46,47] and the third one corresponds to the decomposition of
imide structures [48]. TGA data showed that all the coatings loose
<5% of their initial weight below 150 ◦ C due to volatiles such as
residual solvents and water evolved during imidization reaction.
Fig. 4(a) shows the TGA profiles of representative coatings based
on various chain extenders. The analyzed data suggests that T1ON,
T2ON and Td50 are highest for PMDA chain extender based HBPU
coating and lowest for NHTM based coating. For instance, the T2ON
and Td50 for PU-G2-1.4H-PMDA, PU-G2-1.4H-APTES and PU-G2-
1.4H-NHTM are 187, 183, 181; 263, 256, 249 and 327, 305, 302 ◦ C,
respectively. The above trend is due to the cumulative effect of
more symmetry and larger dipole–dipole interactions in case of the
PMDA based chain extender (four imide groups per molecule) than
others [44]. The increased phase separation and domain cohesion
because of the stronger dipole–dipole interaction of imide groups
present in the hard segment are responsible for the improve-
ment of thermal properties. Fig. 4(b) shows the thermal behavior
of some representative HBPU-imide coatings with increasing the
NCO/OH ratio and the result suggests that higher NCO/OH based
HBPU-imide coatings possess higher thermal stability. For instance,
Td50 and wt.% remaining at 450 ◦ C for PU-G2-1.2H-NHTM and

Scheme 1. The steps involved along with the reaction conditions used for the synthesis of (a) different generation HBPs and (b) HBPU prepolymers.

Please cite this article in press as: A.K. Mishra, et al., Hyperbranched polyurethane (HBPU)-urea and HBPU-imide coatings: Effect of chain extender
and NCO/OH ratio on their properties, Prog. Org. Coat. (2011), doi:10.1016/j.porgcoat.2011.11.027
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Scheme 2. The reaction scheme for the synthesis of different chain extender based HBPU coatings.

PU-G2-1.4H-NHTM are 299, 302 ◦ C and 3.4, 7.2%, respectively. This
trend is might be due to the formation of higher amount of imide
rings in the coating formulation with increasing NCO/OH ratio.
Thus, more energy is needed to decompose the coating films and
thereby increases the thermal stability. The similar result is also
observed in case of different HBPU-urea coatings (see TGA data in
Table 2) with increasing the NCO/OH ratio. This is due to the for-
mation of more number of allophanate or biurate linkages along
with the urethane/urea hard components in the coating formula-
tion [45,49].

Table 2
TGA data of some representative chain extender based HBPU-urea and HBPU-imide coatings.

Sample code T1ON (◦ C) T2ON (◦ C) T2MAX (◦ C) T3ON (◦ C) T3MAX (◦ C) Td10 (◦ C) Td50 (◦ C) Wt.% remaining at
450 ◦ C

PU-G1-1.2H-NHTM 163 231 253 305 386 186 218 5.3

PU-G1-1.2H-PMDA 175 246 264 323 402 197 246 5.8
PU-G1-1.2H-APTES 168 238 281 398 415 210 286 6.8
PU-G1-1.4H-PMDA 173 241 293 372 421 230 302 7.6
PU-G2-1.2H-NHTM 174 246 299 352 392 201 299 3.4
PU-G2-1.4H-NHTM 181 249 300 371 384 223 302 7.2
PU-G2-1.4H-APTES 183 256 302 374 386 234 305 8.8
PU-G2-1.4H-PMDA 187 263 322 385 435 251 327 17.5

Please cite this article in press as: A.K. Mishra, et al., Hyperbranched polyurethane (HBPU)-urea and HBPU-imide coatings: Effect of chain extender
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Fig. 2. The overlapped FTIR spectra of representative HBPU-urea and HBPU-imide cured films in the range of 400–4000 cm−1 and the expanded zone is in situ attached.

3.3. Viscoelastic study PU-G1-1.4H-APTES, PU-G1-1.2H-NHTM, PU-G1-1.2H-PMDA and

Fig. 5(a) and (b), represents the E and tanı vs. temperature
curves of representative HBPU-urea and HBPU-imide coatings by
varying chain extender structure and NCO/OH ratio. The glass
transition temperature (Tg ), storage modulus (E ) and crosslink
density (e ) at (Tg + 5)◦ C data for various HBPU-urea and HBPU-
imide coatings are presented in Table 3. The obtained data suggests
that all were increased with increasing NCO/OH ratio. The PMDA
chain extender based HBPU-imide coating possesses higher Tg
and modulus values than APTES and NHTM based coatings. For
instance, Tg and E at 40 ◦ C for PU-G1-1.4H-NHTM, PU-G1-1.4H-
APTES and PU-G1-1.4H-PMDA are 92.8, 98.8, 131.7 ◦ C and 2.9 × 109 ,
1.36 × 1010 , 1.23 × 1010 [Pa], respectively, while the same for PU-
G2-1.2H-NHTM and PU-G2-1.4H-NHTM, are 100.8, 129.4 ◦ C and
8.48 × 109 , 1.71 × 1010 (Pa), respectively. The above results are due
to the combined effect of formation of more number of hydro-
gen bonded structures between urethane/urea and imide hard
segments (responsible for restricted chain mobility) with increas-
ing NCO/OH ratio and also due to higher symmetry of PMDA
chain extender structure containing four imide −C O groups per
molecule than APTES and NHTM chain extender [39,50].
3.4. Tensile property and contact angle analysis
Tensile property of different chain extender based coatings was
evaluated by UTM instrument in a tensile mode and representative
data is given in Table 4. UTM data suggest that tensile modu-
lus increased and elongation at break decreased significantly with
increasing the NCO/OH ratio and imide content of the coating
formulations [51]. For instance, the tensile strength and % elonga-
tion at break for representative coatings viz., PU-G1-1.2H-APTES,
PU-G1-1.4H-PMDA are 86.4, 106.4, 68.7, 126.7, 165 MPa and 5.0,
4.2, 6.2, 3.7, 2.6, respectively. This could be due to increased phase
separation between imide and urethane/urea hard segments [13] in
case of PMDA chain extender than the others. The higher phase sep-
arated structures in case of PMDA chain extender is because of its
higher symmetry and more polar nature [44]. The increased inter-
action restricts the chain mobility and thus increases the tensile
modulus of the coating film [52].
The surface properties of different chain extender based coat-
ings with increasing NCO/OH ratio and by varying the chain
extender structure were evaluated by measuring the contact angle
formed between water drops and surface of the samples using
G 10 (KRUSS) instrument. For this, average of three concurrent
readings was used for each sample. The contact angle data sug-
gests that PMDA chain extender based HBPU-imide coating is the
most hydrophobic than others and hydrophobicity increases with
increasing NCO/OH ratio. This could be due to more phase separa-
tion between urethane/urea and imide segments in case of PMDA
chain extender because of its higher symmetry and more polar
nature [44]. Due to phase separation, high energy polar compo-
nents (−NH· · ·C O−N−) migrate to the polymer–metal interface,
thus decreasing the surface polarity or increasing the contact angle
[44,53,54]. Contact angle of the samples measured after 10 min
interval of time suggests almost similar values, suggesting that
there is less spreading of water drop on the film surface.
3.5. Solubility, adhesive strength and gel content study
The solubility of HBPU-urea and HBPU-imide films were studied
by putting the rectangular size films in hexane, dichloromethane,
toluene, chloroform, THF and NMP for 7 days. The observation

Table 3
DMTA data of some representative chain extender based HBPU-urea and HBPU-imide coatings.

Sample code Tg in ◦ C E at 40 ◦ C [Pa] E at (Tg + 5 ◦ C) [Pa] Tan ımax C × 10−3 (kg/m3 )

at (Tg + 5 ◦ C)

PU-G1-1.2H-NHTM 90.5 5.14 × 108 1.32 × 108 0.61 14.6

PU-G1-1.2H-PMDA 118.7 7.34 × 109 6.15 × 108 0.52 65.0
PU-G1-1.4H-NHTM 92.8 2.90 × 109 1.83 × 108 0.59 20.1
PU-G1-1.4H-APTES 98.8 1.36 × 1010 5.21 × 108 0.46 56.2
PU-G1-1.4H-PMDA 131.7 1.23 × 1010 1.13 × 109 0.33 112.0
PU-G2-1.2H-NHTM 100.8 8.48 × 109 5.46 × 108 0.56 54.1
PU-G2-1.4H-NHTM 129.4 1.71 × 1010 5.14 × 108 0.43 55.1

Please cite this article in press as: A.K. Mishra, et al., Hyperbranched polyurethane (HBPU)-urea and HBPU-imide coatings: Effect of chain extender
and NCO/OH ratio on their properties, Prog. Org. Coat. (2011), doi:10.1016/j.porgcoat.2011.11.027
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Table 4
Contact angle and tensile properties data of some representative chain extender based HBPU-urea and HBPU-imide films.

Sample code Contact angle in degree Multiple tensile strength Final Tensile strength in % Elongation
readings in MPa MPa (mean ± SD) at break

1st 2nd 3rd

PU-G1-1.2H-NHTM 53 44 66 72 68 (68.7 ± 2.49) 6.2

PU-G1-1.2H-APTES 57 48 85 83 91 (86.4 ± 3.39) 5.0
PU-G1-1.2H-PMDA 61 52 122 131 125 (126.0 ± 3.74) 3.7
PU-G1-1.4H-APTES 68 62 106 103 110 (106.4 ± 2.86) 4.2
PU-G1-1.4H-PMDA 70 67 166 158 171 (165.0 ± 5.35) 2.6
PU-G2-1.4H-APTES 71 64 127 124 129 (126.7 ± 2.05) 4.1
PU-G2-1.4H-PMDA 73 68 178 173 184 (178.4 ± 4.49) 2.2

suggests that samples were not affected in nonpolar solvents like
hexane and toluene, but swelled in chlorinated and polar apro-
tic solvents like dichloromethane, THF and NMP, due to the good
compatibility between urethane/urea and imide hard segments
through hydrogen-bonding (phase separation). Thus, higher the
phase separation, higher will be the number of polar components
and better will be the solubility in common organic solvents [13].
Interfacial adhesion plays an important role from the coating appli-
cation point of view, since good adhesion protects the substrate in
better way form corrosion.
In the present study, adhesive strength of different chain
extender based HBPU coatings has been analyzed and results
are summarized in Table 5. In our earlier publication [44], we
have shown that adhesive strength depends on the surface seg-
regation behavior (due to the phase separation of hard and soft
segments) and chemical interaction or mechanical interlocking at
the metal–polymer interface. The present data suggests that adhe-
sive strength is highest for PMDA-based chain extender coating
than others, and its value increases with increasing the NCO/OH

Fig. 3. (a) and (b) The representative deconvulated (a) −C O and (b) −NH zones,
of HBPU-imide coatings with the variation of anhydride structure. (c and d) The Fig. 4. (a) and (b) Representative TGA thermograms of different synthesized HBPU-
representative deconvulated (c) amide I and (d) −NH zones, of HBPU-urea coatings urea and HBPU-imide coating films by varying the (a) chain extender structure and
with increasing the NCO/OH ratio. (b) NCO/OH ratio.

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Table 5
Coating properties of some representative chain extender based HBPU-urea and HBPU-imide coating films.

Sample code Water resistance Alkali resistance in 5% Adhesive Wt. loss in Gel content
(after 7 d) NaOH solution (after 72 h) strength (kg) mg (%)

PU-G1-1.2H-NHTM PA CS 370 37 73
PU-G1-1.2H-APTES PA CS 420 32 78
PU-G1-1.2H-PMDA NA CS 480 24 86
PU-G1-1.4H-APTES PA CS 460 27 87
PU-G1-1.4H-PMDA NA PS 570 18 93
PU-G2-1.4H-APTES NA CS 510 21 90
PU-G2-1.4H-PMDA NA CS 540 16 92

NA = not affected, PA = partially affected, CS = completely soluble, PS = partially soluble.

ratio [49]. This is due to the more symmetry and higher number
of imide groups per molecule in case of PMDA chain extender,
which increases the accumulation of polar phase separated struc-
tures at the metal–polymer interface [44]. These polar components
bind with the free electrons or positive charged holes present in
the metal through coordinate bonds, thus increasing the adhesive
strength. Similar results are also reflected for abrasion resistance
of different chain-extended HBPU coatings.
Gel content of the coating film was obtained by placing a known
weight of the oven dried film (W1 ) into a soxhlet apparatus for
continuous extraction with toluene for 24 h at 120 ◦ C. The polymer
gel remained after extraction was dried (W2 ) and the degree of
crosslinking was measured in terms of gel content (%). Three test
specimens were used for each sample and average was taken as %
of gel content:
W 
2
Gel content % = × 100%
W1
The data presented in Table 5 suggest that all the samples have
>80% of gel content, which increased with increasing the hard
segment content or NCO/OH ratios due to the formation of more
network structures through hydrogen bonding [55,56].
4. Conclusions
The present study investigates the effect of chain extender type
and NCO/OH ratio on the properties of different HBPU-urea and
HBPU-imide coatings. Initially, HBP-G1 and HBP-G2 were reacted
with excess diisocyanate to obtain a series of NCO-terminated pre-
polymer resins. The excess NCO content of the prepolymer resin
was calculated by standard dibutylamine titration method, which
was completely chain extended by APTES, NHTM and PMDA chain
extenders separately to obtain different HBPU-urea or HBPU-imide
coatings either by moisture or thermal curing process. FTIR decon-
volution results suggest that PMDA-based chain extender coating
possesses higher hydrogen bonding interaction than NHTM and
APTES chain extender-based systems and this interaction increased
with increasing NCO/OH ratios. TGA, DMTA and UTM data support
the FTIR results, i.e., thermal, mechanical and tensile properties are
higher for more symmetrical PMDA chain extender-based coat-
ing system than others. Contact angle data suggest the increase
of hydrophobicity with increasing NCO/OH ratio. The adhesive
strength and gel content are highest for PMDA- based HBPU-imide
coatings.

Acknowledgements

A.K. Mishra would like to thank Council of Scientific and

Industrial Research (CSIR, New Delhi, India) for awarding the
research fellowship. Professor T.M. Aminabhavi thanks CSIR
[21(0760)/09/EMR-II] for Emeritus Scientist fellowship.

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Please cite this article in press as: A.K. Mishra, et al., Hyperbranched polyurethane (HBPU)-urea and HBPU-imide coatings: Effect of chain extender
and NCO/OH ratio on their properties, Prog. Org. Coat. (2011), doi:10.1016/j.porgcoat.2011.11.027