Progress in Organic Coatings 77 (2014) 61–71

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Progress in Organic Coatings

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

Synthesis and characterization of low crystalline waterborne

polyurethane for potential application in water-based ink binder
Changqing Fang a,∗ , Xing Zhou a , Qian Yu a , Shaolong Liu a , Dagang Guo b,∗ ,
Ruien Yu a , Jingbo Hu a
a
School of Printing and Packaging Engineering, Xi’an University of Technology, Xi’an 710048, China
b
School of Material Science and Engineering, Xi’an Jiaotong University, Xi’an 710049, China

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

Article history: Waterborne polyurethane dispersions (PUDs) with low crystallization and narrow nanoparticles
Received 11 April 2013 distribution were synthesized from poly(propylene glycol) (PPG), isophorone diisocyanate (IPDI),
Received in revised form 20 June 2013 dimethylolpropionic acid (DMPA) via a environmental and simple process combined prepolymer iso-
Accepted 19 August 2013
cyanate process with acetone process. For used as ink binder, the acid numbers of PUDs were analyzed.
Available online 16 September 2013
It was found that the acid number changed with the solid content and mainly increased with increasing
hard-/soft-segment molar ratio. Fourier transform infrared (FTIR) spectroscopy, proton nuclear mag-
Keywords:
netic resonance spectroscopy (1 H NMR), transmission electron microscope (TEM), differential scanning
Waterborne polyurethane
Nanoparticles
calorimetry (DSC), thermogravimetric (TG), X-ray diffractometer (XRD) and polarizing optical microscopy
Stability (POM) measurements were utilized to characterize the bulk structures and thermal properties of PUDs.
Low crystallinity The results show that nanoscale waterborne polyurethane dispersions synthesized through the combined
process have good thermal stability and weakly crystallinity, which is suitable for the use of water-
based ink binder. The performance of PUDs can be optimized for the application as ink binder when the
hard-/soft-segment molar ratio is 4 or 5.
Crown Copyright © 2013 Published by Elsevier B.V. All rights reserved.

1. Introduction
During the synthesis of solvent-based ink, the evaporation of
volatile organic compounds (VOCs) causes a variety of health, safety
and air contamination problems. For such reason, water-based ink
is favored in printing and packaging industries. Solvents are the fun-
damental difference between solvent-based ink and water-based
ink. Water-based ink adopts water (45–50% in the total mass) as
solvent. The decrease of VOCs not only prevents air pollution, but
also reduces certain toxic substances containing in organic sol-
vents [1,2]. Therefore, water-based ink has been widely used as
environment-friendly ink in the printing and packaging industries
[3,4]. The compositions of water-based ink are similar to solvent-
based ink, which contain pigment, binder and other additives. The
binder composed of alkali-soluble resin, latex, water and other
accessory solvent plays a connective role in water-based ink. It
distributes pigment granules evenly, imparts the ink certain mobil-
ity and suitable adhesion with printing substrates, and promises
the water-based ink forming a uniform film. The binder directly
affects the using performance of ink, such as viscosity, adhesion,
∗ Corresponding authors. Tel.: +86 29 82312038; fax: +86 29 82312512.
E-mail addresses: fcqxaut@163.com (C. Fang),
guodagang@mail.xjtu.edu.cn (D. Guo).
gloss and drying properties [5,6]. Therefore, a proper binder with
good performance is crucial for water-based ink.
Polyurethane, owning numerous structural features that result
in many useful and intriguing properties [7], was selected as the
proper water-based ink binder in this paper. A large number
of researches have focused on aqueous polyurethane dispersions
(PUDs) due to environmental, health and safety issues in nearly
a decade. For instance, hydrogen bonding and chemically-induced
separation of urethane-rich and urea-rich domains in polyurethane
have been directly observed using X-ray spectromicroscopy [8–14].
But most of polyurethanes are used as coatings for various fibers,
adhesives for alternative substrates, primers for metals, caulking
materials, emulsion polymerization media for different monomers,
paint additives, defoamers, associate thickeners, pigment pastes
and textile dyes [15]. Very little progress has been reported on the
application of PUDs in printing industry.
The polyols, which are mainly of polyesters, polyethers, poly-
caprolactone, and polycarbonate origin, are soft segments in PUDs.
Since polyurethane used as binder should have low crystallinity
and limited molecular weight, and the PUDs synthesized from
PPG have low crystallinity and high climate resistance and water
resistance [16]. PUDs synthesized from PPG are adopted to replace
the ordinary binder in the process of producing water-based ink.
Isophorone diisocyanate (IPDI) is selected for the synthesis of
urethane due to its sufficient stability against water during the

0300-9440/$ – see front matter. Crown Copyright © 2013 Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.porgcoat.2013.08.004
62 C. Fang et al. / Progress in Organic Coatings 77 (2014) 61–71
process. Dimethylolpropionic acid (DMPA) is the most widely used
hydrophilic chain extender for the steric hindrance of COOH
group; as a consequence, its interaction with isocyanates is min-
imized [17]. Both diamines and diols can be a chain extender.
Diamines release excitant odour, which is unfavorable for envi-
ronment and health. Therefore, 1, 4-butanediol (BDO) is chosen as
the chain extender. Since organo-tin compounds are very effective
for the catalysis of isocyanate-hydroxyl reaction and the catalyst
used in this study should not to be too hydrophilic [18], dibutyltin
dilaurate (DBTDL) is selected to catalyze the isocyanate-hydroxyl
reaction.
In our experiments, a suitable relative humidity (RH) has to
be ensured. Low RH favors high glass transition temperature (Tg )
of polyurethane dispersions, since low RH conditions result in
increased urethane and decreased urea content [8]. Additionally,
binder with a relatively low Tg is good for printing, thus, RH is
set to be 70%. A two step procedure which combines prepolymer
isocyanate process with acetone process had been taken to obtain
PUDs [15,19–21], although a recently research reports that PUDs
can be synthesized via a one-step procedure using a miniemulsion
process [22], the synthesized polyurethane has a high molecule
weight [18] and it is hard to control the simultaneous reactions of
isocyanate/hydroxyl and isocyanate/water in one-step procedure.
In this study, several aqueous PUDs were synthesized from
poly(propylene glycol) (PPG) with high solid contents and low
Brookfield viscosity to produce water-based ink binders. It is
noteworthy that the acid number is one of the most impor-
tant performances of binder’s. A large acid number will cause an
enhancement of the viscosity of ink, even a retrogradation. While
a small value may result in a poor wettability to pigment of the
binder and a poor flow properties and glossiness of the ink. Accord-
ing to the binders of Bayer (i.e. Bayhydrol U 241, Bayhytherm 3146),
the acid number is mostly in the range of 6.0–9.0 mg of KOH/G,
which is suitable for water-based ink. When water-based inks are
shipped during cold weather, they may experience cycles of freez-
ing and thawing, leading to more damage of water-based inks
than when the inks are subjected to steady freezing. Therefore,
the freeze–thaw stability should be monitored under the cycles of
freezing and thawing. Moreover, other properties, such as the elec-
trolytic stability, thermal stability, swelling, particle size, etc. are
also characterized.
2. Experimental
2.1. Materials
The diisocyanate used was isophorone diisocyanate (IPDI,
98 wt% purity, purchased from Jingchun Chemical, Shanghai, China)
which is liquid at room temperature. Poly(propylene glycol) (PPG,
molecular weight (Mw) = 2000, acid value ≤ 0.08 mg of KOH/G,
hydroxyl value = 54–58 mg of KOH/G, dried under vacuum, at
120 ◦ C) and dimethylolpropionic acid (DMPA) (both purchased
from Jingchun Chemical, Shanghai, China) were used as oligomer
glycol and hydrophilic chain extender. 1, 4-Butanediol (BDO,
99.5 wt% purity), triethylamine (TEA, 99 wt% purity), and 1-methyl-
2-pyrrolidone (NMP, 99 wt% purity) were purchased from Fuchen
Chemical, Tianjin, China. Dibutyltin dilaurate (DBTDL) was pur-
chased from Qingxi Chemical, Shanghai, China. Acetone about
15–20 mL was used throughout the process and deionized water
was used as dispersing phase at last.
2.2. Synthesis of waterborne polyurethane dispersions
Three aqueous PUDs with different molar ratios of isocyanate
groups to oligomer polyols hydroxyl groups (hard-/soft-segment
molar ratio of 3, 4, and 5, respectively) were synthesized with
Table 1
Recipe for the preparation of polyurethane dispersions (weight in g).
Sample Ingredient
IPDI PPG-2000 DPMA NMP BDO TEA
PU3 16.664 49.626 3.570 5.984 0.990 2.912
PU4 22.285 50.285 3.966 6.637 2.679 2.974
PU5 27.769 50.043 4.325 7.166 4.328 3.26
the appropriate NCO/OH ratio of 1.2. The DMPA content was set
to be 5 wt% (with respect to the prepolymer weight) [13]. PPG
and IPDI were added to a four-necked flask (500 mL) equipped
with a mechanical stirrer, thermometer and spiral condenser in
an electric-heated thermostatic water bath. The reaction was car-
ried out at 80 ◦ C for 2.5 h, then DBTDL was added when the first
reaction had occurred for 2 h, followed by the addition of DMPA
dispersed in NMP at 60 ◦ C. The reaction was continued at 80 ◦ C for
another 2 h. Subsequently, the resulting prepolymer was cooled to
about 35 ◦ C, and then BDO with a small amount of acetone and
TEA in 120 g of deionized water were poured into the flask. In
the all process, a moderate amount of acetone was used to reduce
the viscosity. After the reaction, the residual acetone was removed
in a vacuum drying oven at 50 ◦ C and 0.05 MPa for 1 h. The gen-
eral recipe used for the preparation of polyurethane dispersions is
listed in Table 1. Scheme 1 shows the process for synthesis of our
waterborne polyurethane dispersions.
2.3. Preparation of PUDs films
The films were obtained by casting the PUDs onto Teflon sur-
faces, a slow evaporation of the solvent at room temperature for 3
days and then at 40 ◦ C in a vacuum drying oven for 12 h to allow
the complete removal of solvent. Then, the films with Teflon were
stored in a desiccator to avoid moisture.
2.4. Measurements
Solid content measurement was carried out according to ISO
124:1997 standard. About 1.5 g of PUDs was placed in a glass garden
with a diameter of 60 mm. The solid content of every sample was
calculated as the average of three measurements of weight before
and after water evaporation.
Brookfield viscosities of the PUDs were obtained using Brook-
field viscometer DV-II+ (Brookfield Engineering Laboratories,
Stoughton, MA, USA). About 250 mL of sample was placed in a
beaker at a room temperature of 25 ◦ C and using the spindle no.
61 with a stirring speed of 100 rpm. The Brookfield viscosity of
every sample was calculated as the average of three experimental
determinations.
The pH values of the PUDs were measured at room temperature
in a pH-meter using a silver reference electrode model HI 8418
(Hanna Instruments) at a room temperature of 25 ◦ C. The pH was
calculated as the average of three experimental determinations.
Acid number of PUDs was measured and calculated accord-
ing to ISO 2114:2000 standard. The indicator titration in part A
was carried out in the measurement. Phenolphthalein indicator
dissolved in ethyl alcohol as the standard described was pre-
pared.
The mean particle size and the particle size distribution of the
PUDs were measured in Coulter LS230 system (Beckman Coulter,
Miami, FL, USA), provided with laser diffraction and polarized light
detectors. A small amount of sample was added into the deionized
water tank. The statistical model used to obtain the particle size
distribution assumed that the particles were polystyrene and took
into account the refraction index of the polystyrene (1.6) and the
 C. Fang et al. / Progress in Organic Coatings 77 (2014) 61–71
Scheme 1. Synthesis route of waterborne polyurethane dispersions.
water. The mean particle size was calculated as the average of two
experimental determinations.
The electrolytic stability was measured by mixing 5 mL of PUDs
and 5 mL of deionized water in a beaker (50 mL), an aqueous solu-
tion of 2 M NaCl was slowly dropped into the beaker through a
burette (50 mL) until coagulation was obtained. The electrolytic sta-
bility was measured by the volume of NaCl necessary to coagulate
the PUDs. The values of all samples obtained were the average of
three replicates.
The freeze–thaw stability was performed according to ASTM
D2243-95 standard. The PUDs were put into three pint-size
(250 mL) glass bottles. All of them were subjected to cycles of freez-
ing and thawing at a temperature of −18 ◦ C (0 F). When taken out
from the refrigerator, the samples were allowed to stand for 7 h
undisturbance at room temperature, and then rating any evidence
of settling, gelation and coagulation.
The shelf stability was determined by placing all samples in fine
glass bottles setting undisturbed on a shelf at room temperature.
Fourier transform infrared (FTIR) spectroscopy measurement
was used to identify the structure of PUDs, the infrared spec-
tra of the dried polyurethane films were obtained with a Fourier
Transform IR spectrophotometer (SHIMADIU FTIR-8400S (CE)) and
recorded in the transmission mode at room temperature by averag-
ing 20 scans at a resolution of 16.0 cm−1 . The spectra were analyzed
in the frequency range of 4000–400 cm−1 .
Proton nuclear magnetic resonance spectroscopy (1 H NMR)
spectra were obtained on a Bruker-400MHz spectrometer, using
sodium 2, 2-dimethyl-2-silapentane-5-sulfonate (DSS) as an inter-
nal standard, with D2 O (0.5 mL) as solvent.
Transmission electron microscope (TEM) was performed using
a JEM-3010 microscope working at accelerating voltage of 200 kV.
63
The samples were prepared through diluting one drop dispersion
with 30 mL deionized water.
Thermogravimetric (TG) experiments were carried out in a MET-
TLER TOLEDO TGA/DSC 1 analyzer with Gos Controller GC10 STARe
System. Film samples ranging from 4 to 10 mg were placed in
an alumina ceramic crucible and heated under argon (flow rate:
100 mL/min) from 30 to 700 ◦ C with a heating rate of 15 ◦ C/min.
Differential scanning calorimetry (DSC) experiments were car-
ried out in METTLER TOLEDO DSC 823e with a temperature range
from −50 to 200 ◦ C at a heating rate 10 ◦ C/min under a argon atmo-
sphere (flow rate: 50 mL/min).
An X-ray diffractometer (XRD) instrument (XRD-7000, Shi-
madzu Limited, Japan) was used to analyze the crystallinity of
the polyurethane films with monochromatic Cu K˛ radiation
(1.540598 nm). A scanning of 2 angles between 10◦ and 60◦ under
the scan speed of 8.0000 deg/min was carried out.
Polarizing optical microscopy (POM) crystalline morphology
of the samples was studied at room temperature using com-
pound polarized light microscopy (Leica LABORLUX 12POL, Leica
Microsystems GmbH, Wetzlar, Germany) attached with charge
coupled device (CCD) color camera (KY-F550E, Victor Company of
Japan Limited (JVC), Kanagawa-ku, Yokohama, Japan).
The swelling [23,24] was measured by immersing the PUDs films
in beaker with deionized water at room temperature. The percent-
age of swelling for a particular film was determined by measuring
its weight changes.
W − W0
%swell = × 100, (1)
W0
where W0 is the weight of the dried film and W is the weight after
water absorption.
64 C. Fang et al. / Progress in Organic Coatings 77 (2014) 61–71

12 Table 2
Some properties of the waterborne polyurethane dispersions.
PU5
Sample Solid content Brookfield viscosity pH Acid number
10 (wt%) (mPa s) (mg KOH/g)
PU4 PU3 33.5 21.5 6.5 7.233
8 PU4 33.6 21.4 7.0 8.132
PU5 36.5 55.4 7.0 8.655
NaCl (ml)

6 PU3
3. Results and discussion
4
3.1. Characteristics of the dispersions

2
The solid content, Brookfield viscosity, pH and acid number of
the PUDs samples are listed in Table 2. All samples show relative
0 high solid content and low viscosity, which are good for the drying
3 4 5 of binder and the dispersion to pigment. The pH values of PUDs are
NCO/OH 6.5–7.0. When increasing the molar ratio of hard-/soft-segment, the
solid content and acid number mainly increase. We suggest that
Fig. 1. Electrolytic stability of PUDs with different hard-/soft-segment molar ratio. acid number is decided by the content of DMPA, which increases
as the hard-/soft-segment molar ratio (molar ratio of 3, 4 and 5)
increases. While the viscosity decreases as the molar ratio of hard-
/soft-segment is lower than 4. The slightly decrease of viscosity
with the molar ratio of hard-/soft-segment is lower than 4 may be
due to the increase of NMP content. The all samples acid numbers

Fig. 2. TEM images of the dispersions of (a) PU3, (b) PU4, and (c) PU5.
 C. Fang et al. / Progress in Organic Coatings 77 (2014) 61–71 65

10 30
PU3 PU4
25
8
Mean particle 20
size=1.83 µm Mean particle
6

Volume (%)
Mean particle size=77 nm
Volume (%)

size=671 nm 15
4 Mean particle
size=81 nm
10

2 5

0 0
0.04 0.4 4 40 400 0.04 0.4 4 40 400
Particle Diameter (µm) Particle Diameter (µm)

25
PU5
20
Mean particle
size=68 nm
15
Volume (%)

10
Mean particle
size=174 nm

0
0.04 0.4 4 40 400
Particle Diameter (µm)

Fig. 3. Particle size distributions of the PUDs with different hard-/soft-segment molar ratio.

are in the range of 7–9 mg of KOH/g, which is suitable for the water-
borne ink binder.
3.1.1. Stability of the dispersions
As for the shelf stability, a film formed on the surface of PU3 sam-
ple and the film gradually dissolved in the emulsion after a week,
besides the viscosity (the value is 973.2 mPa s) of PU3 increased
markedly, indicating the PU3 a poor shelf stability. It may due to
a wide particle size distribution of PU3. No obvious change was
observed in PU4 and PU5.
Fig. 1 shows the volume of NaCl solution required to coagu-
late the PUDs. It is known that the addition of strong electrolytes
causes the unstabilization of the double electrical layers in ionomer
particles, which facilitates the rupture of the dispersion [13]. The
larger the molar ratio of hard-/soft-segment, the higher the volume
of NaCl is required. Therefore, the electrolytic stability resistance
increases as the molar ratio of hard-/soft-segment increases.
After completion of the cycles of freezing and thawing, the sam-
ple of PU3 gelated completely after 2 times cycles, PU5 coagulated
completely after 3 times, while PU4 gelated completely after 6
times. The levels of the PU3 and PU5 are considerable according
to ASTM D2243-95 (2008), while the PU4 is slight. The differences
in all samples may be attributed to the size distribution. The wide
size distribution of PU3 and PU5 results in a tendency of gelation
for the sample, and the gelation intensifies along with the cycles of
freezing and thawing, which shows poor freeze–thaw stability. Due
to the narrow size distribution of PU4, it shows good freeze–thaw
stability.
3.1.2. Morphology and particle size of the dispersions
Fig. 2 is the TEM images of the particle morphology and
size for the PU3, PU4 and PU5 dispersions. According to
the previous researches [25–27], the hydrophilicity, prepoly-
mer viscosity, ionic group position, chain rigidity, Mn of the
oligomer polyol and the chemical structure of the soft seg-
ment have an influence on the particle morphology and size.
As Fig. 2 depicted, PU4 and PU5 dispersions have apparently
spherical particle size, while PU3 dispersion is different from
PU4 and PU5. The difference indicates that hard-/soft-segment
ratio in this study play a role in influencing the particle morphology.
It reveals that only the dispersions prepared with the hard-/soft-
segment molar ratio of not less than 4 have spherical particle size
dispersed in water.
Fig. 3 shows the particle size distributions of PUDs with different
hard-/soft-segment molar ratios. The particle size of the specimens
decreases as the hard-/soft-segment ratio increases. Moreover, the
samples, especially for PU4 and PU5, have a narrow particle size
distribution, indicating that the most particles are small (about 68
and 77 nm, respectively). However, the particle distribution of PU3
is wide and heterogeneous and the particle has a higher size, which
directly results in poor shelf stability. Generally, when the particle is
similar to spherical, the particle size, related to dispersion viscosity,
can be expressed by a power law,
rel = 1 + k1 ˚ + k2 ˚2 + · · ·, (2)
where rel is the ratio of dispersion viscosity to that of medium,
k1 is the Einstein constant (2.5) and ˚ is volume fraction of
66 C. Fang et al. / Progress in Organic Coatings 77 (2014) 61–71

particles. However, under motion ˚ is replaced by the effective

volume fraction, ˚eff , given by
PU3
˚eff = f˚, (3)

where

Relative transmittance
 3
Dp + 2ı PU4
f= , (4)
Dp

The hydrodynamic increment of the particle radius, ı, increases

as the particle size (diameter Dp ) decreases. PU5
From the formulas above, the Dp increases as the increase of the
rel . The viscosity of PU4 is 21.4 mPa s while the PU5 is 55.4 mPa s
(Table 2), and the larger viscosity of PU5 results in a relative large
Dp . The Dp of PU3 is anomalistic due to its wider particle size dis-
tribution shown in Fig. 3.
The wide particle size distribution in the PUDs could be 4000 3500 3000 2500 2000 1500 1000 500
attributed to excessive viscosity of the prepolymer during the dis- Wavenumber/cm
-1

persion step in the synthesis procedure, making the dispersion of

the prepolymer more difficult, which inhibits the fragmentation
of the polymer into smaller particles in water [28]. According to
PU4 and PU5, the mean particle size in volume of the PUDs is
slightly increased by increasing the IPDI content. Therefore, it can
be expected that the higher the particle size of the dispersion, the
higher the solid content and the lower the viscosity. The results of
this study are in agreement with the previous [21,29]. Compared
PU3 and PU4, the particle size distribution of them is dramati-
cally different though the solid content and viscosity are nearly the
same. The particle size increases and the particle size distribution
becomes wider for the hard-/soft-segment molar ratio lower than
4. The higher of the hard segment results in a higher ionic content
on the polymer. The smaller particle size and narrower particle size
distribution of PU4 may arise from the increase of DMPA content,
which gives rise to high hydrophilicity of the polyurethane ionomer
[13].
In general, films with better appearance and mechanical prop-
erties can be obtained by using small latex particles. Small PUDs
particles are desirable when deep penetration of the dispersion into
a substrate is essential [15]. Therefore, nanosized PUDs particles are
more attractive in both research and for end-use application [30].
In the printing procedure, printing substrates absorb ink to accel-
erate the speed of drying. Used for ink binder, the smaller of the
PUDs size, the faster for the drying, and the better for printing. In
this study, nanosized PU4 particles (77 nm) with good size distri-
bution were synthesized, which are promising for application in
water-borne ink binder.
Fig. 4. FTIR spectra of PPG-based PUDs with different hard-/soft-segment molar
ratio.
The structure and 1 H NMR results [33] of the samples are shown
in Fig. 5. As depicted in Fig. 5(a), peaks at 1.89, 3.47 ppm are assigned
to the methylene protons of CH2 CH2 O , CH2 CH2 O in BDO
blocks, respectively. Peaks at 1.01, 3.05, 3.35 ppm are assigned to
the methyl, methyne and methylene protons in PPG blocks, respec-
tively. Two sharp peaks at 2.08 and 2.67 ppm are attributed to the
CH3 adjacent to the CH2 NH on the alicyclic and the methy-
lene protons of CH2 NH COO , respectively. Other peaks are
assigned to correspond to the structure in Fig. 5(a). Due to the effect
of D2 O exchange, two extremely weak peaks at 6.55 and 7.33 ppm
may be attributed to CH2 NH COO and NH COO CH2 linked
with alicyclic, respectively. It is obviously that the all samples have
a similar structure from Fig. 5(b). In addition, two weak peaks at
8.30 and 9.52 ppm can be observed in Fig. 5(b), which may be
attributed to NHCONH and NHCONCONH units, respectively.
The presence of NHCONH and NHCONCONH units is consid-
ered to be the reason for the side reaction during the synthesis of
polyurethane. It confirms that there are urea and biuret in the all
samples. These results are corresponding with the FTIR analysis.
Moreover, it is obvious that the intensity of the peaks at 8.30 and
9.52 ppm in Fig. 5(b) is in the order of PU3 > PU5 > PU4, indicating
that the amount of side products is the largest in PU3 and the least
in PU4. This may be one of the reasons that PU3 has a poor stability,
while PU4 show the best stability.

3.2. Structures of the films

Table 3
Characteristic IR bands of the PUDs.
The chemical structure of PUDs was analyzed through FTIR spec-
troscopy. It is obvious in Fig. 4 that the FTIR spectra of the PUDs with Wavenumber (cm−1 ) Assignment Groups assignment
different hard-/soft-segment molar ratios are quite similar. The 3332 st N H (bonded) Urethane
assignment of the most characteristic IR bands is listed in Table 3
2970–2840 st C H Polyol
[31]. It is known that the N–H stretching at 3332 cm−1 , C–N stretch-
ing and ı N–H stretching at 1542 cm−1 , C–H stretching from 2865 2270 st N C O Urethane (free)
1712 st C O Urethane (bonded)
to 2972 cm−1 and C O stretching from 1640 to 1712 cm−1 .
Hydrogen bonding (H-bonding) has been founded in FTIR spec- 1700–1658 st C O Urea (free)
tra of PU [32]. As depicted in Fig. 4, the peak at 3332 cm−1 , assigned 1640 st C O Urea (bonded)
to the hydrogen-bonded NH groups with urethane carbonyl groups, 1542 st C N + ı N H Urea
indicates that most of NH groups form H-bonding with carbonyl 1458 ı CH2 Polyol

oxygen. Meanwhile, the carbonyl stretching band regions in uret- 1450–1400 st (sym) COO− Polyol
hane and urea, the peaks of which should be at 1743 cm−1 and 1242 st (asym) N CO O + st C O C Urethane and polyol
1700 cm−1 , display peaks at 1712 cm−1 and 1640 cm−1 . The change
1103, 955 st C O C Polyol
of the band locations can be attributed to the existence of H-
1018 st (sym) N CO O Urethane
bonding. The existence of H-bonding also can result in a significant
st: stretching, ı: bending, sym: symmetric, asym: asymmetric.
phase separation formed between the soft- and hard-segments.
 C. Fang et al. / Progress in Organic Coatings 77 (2014) 61–71 67

Fig. 5. (a) Structure and 1 H NMR spectrum of PU3; (b) 1 H NMR spectrum of the all samples, (1) PU3, (2) PU4, (3) PU5.

3.3. Thermal and crystallinity analysis of the films
The thermal properties of the PUDs were studied by DSC. Fig. 6
is the DSC thermograms of three investigated polymer samples,
and all of them show the single glass transition temperature in the
range from −45.2 to −41.3 ◦ C, indicating crystallization for all sam-
ples. In our experiments, the contents of PPG (which constitutes
the soft-segment in the PUDs) for all samples were the same. The
Tg is the same for these three samples, which may be ascribed to the
same soft-segment content. Meanwhile, the Tg of soft-segments are
68 C. Fang et al. / Progress in Organic Coatings 77 (2014) 61–71

(a) 2
100
Weight loss

Deriv. weight change (wt%/°C)

Deriv. weight change
EXO

80

Weight loss (wt%)

60
0
Heat Flow

40
PU4
20
PU5

PU3 0 -2
100 200 300 400 500 600 700
Temperature (°C)
-50 0 50 100 150 200 250

Temperature (°C)
(b) 100
Fig. 6. DSC thermograms of PUDs with different hard-/soft-segment molar ratio.
PU3
PU4
80 PU5
substantially higher than that of pure PPG (Mn = 2000, about −69 ◦ C

Weight loss (wt%)

[34]). The increase in Tg demonstrates that the hard-segment dis-
persed in the soft-segment microdomains. The Tm values of the
soft-segments of all samples were not detected in the curves, indi-
cating that the crystallization was very slow, due to the weak phase
separation between soft- and hard-segment [13]. This has been
corroborated by the FTIR spectra with H-bonding.
There are others endotherm transitions temperatures listed in
Table 4. According to Wang and Cooper [35], three characteris-
tic endotherm transitions observed at 60–80 ◦ C, 120–190 ◦ C and
200 ◦ C correspond respectively to the short range, long range and
microcrystalline ordering of hard-segment domains. It can be seen
that the temperatures of Ts , Tl and Tmi are roughly in the order of
PU4 > PU5 > PU3, suggesting that the hard-segment of PU4 has the
best thermal performance among them. In addition, a peak can be
found at about −4.7 ◦ C in the PU4 curve (not in PU3 or PU5 curve),
which may be attributed to the devitrification existing in PU4. This
implies that a nucleating phase of crystal structure should exist in
PU4 during the scanning and the crystal size is small [24].
The thermal resistance of the aqueous polyurethanes (Fig. 7)
was analyzed by TG. Not only can the information of the thermal
stability but also of the structure of PUDs be corroborated by the
TG. Fig. 7(a) shows the TG and derivative of the TG (DTG) curves of
PU3, and Fig. 7(b) is the TG curves of all samples in this study [36].
Before the decompositions, the residual water in PUDs is removed
at 150–180 ◦ C. As the temperature increases, three main stages
appear in Fig. 7(b). Due to the utilization of diol and a diamine,
two kinds of hard segments (urethane and urea) form in the PUDs,
which correspond to the structure showed in Table 3. It is known
that the urethanes have lower thermal resistance than that of the
urea [13,21]. Therefore, the first decomposition process occurring
at 214–222 ◦ C should correspond to the urethane hard-segments,
and the second to those of urea.
Table 4
Endothermic transitions temperatures of all samples.
Sample Ts (◦ C)a Tl (◦ C)b Tmi (◦ C)c
PU3 65.4–66.5 154.1–162.0 184.2–192.1
PU4 74.5–79.3 159.0–174.9 197.3–206.3
PU5 65.0–67.0 158.0–175.0 198.4–206.1
a
Short range of hard segment endothermic transition temperature.
b
Long range of hard segment endothermic transition temperature.
c
Microcrystalline ordering of hard segment endothermic transition temperature.
60
40
20
0
100 200 300 400 500 600 700
Temperature (°C)
Fig. 7. (a) TG and DTG curves of PU3; (b) TG curves of the three investigated polymer
samples.
Table 5 shows the decomposition temperature and weight
loss percentage for each process. The urea content in the hard-
segment is obviously much higher than the urethane, thus, all
the samples have a good thermal resistance performance. This
result suggests that residual NCO groups increase as the ratio of
hard-/soft-segment increases and the residual NCO in polyurethane
particles does not react with the chain extender completely, due
to the high viscosity of particles at low temperature (35 ◦ C) in the
chain extension step which makes it difficult for chain extenders to
diffuse into the particle. Therefore, the residual NCO groups react
with water obtaining more urea.
As shown in Table 5, the percentage of hard-segment content
increases and soft-segment content decreases as the hard-/soft-
segment molar ratio increases, resulting in the increase in the
thermal resistance of hard-segment. The decomposition of the soft-
segment (mainly composed of polyol) is produced at 340–360 ◦ C,
and the weight loss decreases with increasing hard-/soft-segment
molar ratio. Moreover, the thermal resistance of soft-segment of
PU4 is the lowest, which may be attributed to the stronger mixing
of soft- and hard-segment in PU4, and the hard-segment decreases
the thermal resistance of the soft-segment. From Table 5, the
thermal resistance of the hard-segment (urethane and urea) is pro-
portional to the weight loss during the decomposition, while the
soft-segments in PU3 and PU5 are inversely proportional to the
weight loss. According to the initial onset temperature of all sam-
ples, the thermal resistance performance of PU4 is the best.
 C. Fang et al. / Progress in Organic Coatings 77 (2014) 61–71 69

Table 5
Main decomposition of the samples.

Samples First decomposition Second decomposition Third decomposition

T1 (◦ C) Weight loss (wt%) T2 (◦ C) Weight loss (wt%) T3 (◦ C) Weight loss (wt%)

PU3 214.1 6.4% 269.5 22.5% 347.9 63.3%

PU4 221.7 8.1% 272.4 23.6% 340.4 58.4%
PU5 216.3 8.0% 274.9 30.4% 356.5 52.9%

T1 , T2 and T3 are the onset temperatures for the first, second and third decomposition.

800 crystallinity, which should be the characteristic of the soft seg-

ments in polyurethane [37,38]. Moreover, as Fig. 8 depicted, the
700 PU3 intensity of the diffraction peaks decreases with increasing hard-
PU4 /soft-segment molar ratio, indicating a decrease in crystallinity. It is
600 PU5 obvious that the sample PU3 shows a higher crystallinity, indicat-
ing that relative amount of oligomer polyol facilitates crystallinity
500
Intensity (a. u)

in polyurethane. The phenomenon of crystallinity of all samples

can be also demonstrated by POM micrographs at 630× magnifi-
400
cations shown in Fig. 9. It is obvious that the films of all samples
300 are crystalline and the crystallizations are weak, corresponding to
the results of DSC and XRD measurements. The size of crystalline
200 form of all samples is in the order of PU3 > PU4 > PU5, and the crys-
tallizations are imperfect. It may be the result of the decrease of
100 the molar mass of soft segment (PPG), and the hard segment con-
fines the crystallization and destroys the crystalline perfection of
0 soft segment in PUDs.
0 10 20 30 40 50 60 70
2 Theta (°)
3.4. Swelling of the films in water
Fig. 8. X-ray diffractograms of the polyurethane with various hard-/soft-segment
molar ratio. The swelling of the films in water with aging time was shown
in Fig. 10. The best fits were obtained using a sigmoidal sum. It is
The crystallinity of the samples was demonstrated by X-ray evident that the swelling rate and saturated swollen weight are by
diffraction and polarizing optical microscopy. As shown in Fig. 8, far the greatest for PU5 while the smallest for PU3. The absorp-
two diffraction peaks at 2 values of 18◦ (main diffraction peak) tion of water may be attributed to the localized polarity and a
and 42◦ suggesting that the samples have a reduced degree of number of ionic groups at the surfaces. The rate and the weight

Fig. 9. POM microphotographs of samples (a) PU3, (b) PU4, and (c) PU5.
70 C. Fang et al. / Progress in Organic Coatings 77 (2014) 61–71

2.4 [5] K. Alexander, B.M. Matti, A. Shai, M. Shlomo, Ink-jet printing of metallic
nanoparticles and microemulsions, Macromol. Rapid Commun. 26 (2005)
2.2 281–288.
2.0 [6] R. Maria, F. Andrew, Print quality and resistance for water-based flexogra-
phy on polymer-coated boards: dependence on ink formulation and substrate
1.8 PU3 pretreatment, Prog. Org. Coat. 57 (2006) 183–194.
1.6 PU4 [7] D.B. Otts, M.W. Urban, Heterogeneous crosslinking of waterborne two-
component polyurethanes (WB 2K-PUR); stratification processes and the role
PU5
1.4
Swelling (%)

of water, Polymer 46 (2005) 2699–2709.

1.2
1.0
0.8
0.6
0.4
0.2
0.0
0 20 40 60 80 100 120 140 160
Time (h)
Fig. 10. Swelling of the cast films with various hard-/soft-segment molar ratios.
increase with increasing hard-/soft-segment molar ratio, indicating
that the increase in hard-/soft-segment ratio is helpful for the local-
ized polarity and ionic groups exposing to the surfaces. The time of
swelling equilibrium for the all samples varies in Fig. 10; the equi-
librium of PU5 appears after about 40 h immersions in water, PU4
after about 90 h, and PU3 after about 140 h. This result reflects that
IPDI in PUDs yields urethane and urea groups (about 38% accord-
ing to Table 4), which form H-bonding hard phase to retard water
absorption.
4. Conclusions
Poly(propylene glycol)-based waterborne polyurethane with
nanoparticles and weak crystallization have been successfully syn-
thesized via the combination of prepolymer isocyanate process
and acetone process. It shows good performances while the molar
ratio of hard-/soft-segment is 4 or 5. As the ratio increases, the
solid content, viscosity, acid number, electrolytic and storage sta-
bility increase roughly. H-bonding and crystallinity, which affect
the phase separation and thermal properties, have been detected
by FTIR, DSC, XRD and POM, respectively. The PU4 particles with
the narrowest size distribution and diameters of 77 nm has the best
stabilities (i.e. thermal stability and storage stability), relative high
solid content, low viscosity, suitable acid number and crystallinity,
and good water resistance. This result implies that this type of
PUDs in our experiments is potential application in water-based
ink binder.
Acknowledgements
The authors acknowledge the financial support provided by
Shaanxi Programs for Science and Technology Development (Fund
No. 2010K01-096) and Programs for Science and Technology of
Education Department of Shaanxi (Fund No. 2010JK748).
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