Progress in Organic Coatings 76 (2013) 14841493

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Progress in Organic Coatings

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Coatings prepared from waterborne polyurethane dispersions

obtained with polycarbonates of 1,6-hexanediol of different
molecular weights
Vanesa Garca-Pacios a , Jos Antonio Jofre-Reche a , Vctor Costa b ,
Manuel Colera b , Jos Miguel Martn-Martnez a,
a
b

Adhesion & Adhesives Laboratory, University of Alicante, 03080 Alicante, Spain

UBE Chemical Europe, Zona El Serrallo, 12100 Grao (Castelln), Spain

a r t i c l e

i n f o

Article history:
Received 12 January 2013
Received in revised form 15 April 2013
Accepted 4 June 2013
Available online 4 July 2013
Keywords:
Waterborne polyurethane dispersion
Polyurethane coatings
Coatings properties

a b s t r a c t
Waterborne polyurethane dispersions (PUDs) were synthesized with polycarbonates of 1,6-hexanediol of
different molecular weight (5003000 Da) and their properties, adhesion (Hatch adhesion) and coatings
on stainless steel properties (Pencil hardness, Persoz hardness, gloss at 60 , chemical resistance, yellowness index) were characterized. The hatch adhesion of the polyurethane coatings to stainless steel
was very good and decreased slightly by increasing the molecular weight of the polycarbonate of 1,6hexanediol. Both the Pencil and Persoz hardness values of the coatings increased by increasing the hard
segments content in the polyurethane, i.e. by decreasing the molecular weight of the polycarbonate of
1,6-hexanediol, whereas the gloss and the yellowness index were lower for the coatings obtained with
the polycarbonate of 1,6-hexanediol of molecular weight of 500 Da. Very good chemical resistance against
ethanol for all polyurethane coatings on stainless steel plates was obtained but for long time of ethanol in
contact with the coating surface the chemical resistance decreased, more markedly for the polyurethane
coating obtained with the polycarbonate of 1,6-hexanediol of higher molecular weight. In summary,
the segmented structure of the waterborne polyurethane dispersion determined the properties of the
polyurethane coatings obtained from them.
2013 Elsevier B.V. All rights reserved.

1. Introduction
Aqueous polyurethane dispersions (PUDs) used as adhesives or coatings are current real alternatives in the reduction
of volatile organic compounds emissions in industry [1,2] as
they present most of the features of the conventional solventborne polyurethanes and additional properties, such as enhanced
mechanical properties and excellent adhesion [3]. PUDs are mainly
used as exible coatings for textiles and hard coatings for wood and
metallic surfaces [4]. Waterborne polyurethane dispersion consists
in linear thermoplastic polyurethane chains dispersed in water due
to the presence of ionic groups in their structure, which act as internal emulsier. Typically, the acetone procedure is used for PUD
synthesis, the polyol being one important reactant determining
several properties (exibility, adhesion, etc.). Several polyols can
be used for manufacturing PUDs including polyesters, polyethers,
polycarbonate diols and renewable source based polyols [5].

Corresponding author. Tel.: +34 96 5903977; fax: +34 96 5903454.

E-mail address: jm.martin@ua.es (J.M. Martn-Martnez).
0300-9440/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.porgcoat.2013.06.005

Polycarbonate polyols (PCD) has been extensively used to

manufacture biocompatible biomaterials with high mechanical properties. The use of polycarbonate diols, as compared to
polyester and polyether, imparts better hydrolysis resistance, good
elastomeric properties, higher mechanical properties, improved
resistance at low temperature, improved ageing and oil resistance,
and increases the weathering and fungi attack of the polyurethanes
[6,7].
The properties of the thermoplastic PUDs are mainly determined by the interactions between the hard and soft segments,
and by the interactions between the ionic groups [5]. The soft segments (i.e. polyol chains) impart the exibility to the polyurethane,
whereas the hard segments (formed by reaction of the isocyanate
and the chain extender) are stiff and more polar, and have lower
molecular weight. Because the hard segments are covalently
coupled to the soft segments, they inhibit plastic ow of the
polymer chains. Upon mechanical deformation, the hard segments
become aligned contributing to improve polyurethane mechanical
properties. Previous studies [615] demonstrated that the ionic
group content, segmented structure, molecular weight of the
polyol, the type of chain extender and the hard/soft segments
ratio determined the PUDs properties. However, there are few

V. Garca-Pacios et al. / Progress in Organic Coatings 76 (2013) 14841493

studies dealing with the synthesis and characterization of PUDs

and polyurethanes prepared with polycarbonate diols [1622].
In our previous publications, the inuence of the NCO/OH ratio
and the solids content on the properties of the PUDs, polyurethanes
and coatings were studied [2022]. A decrease in the NCO/OH ratio
produced an increase in the mean particle size as well as a decrease
in the Brookeld viscosity of the PUDs. Furthermore, the greater
was the NCO/OH ratio the higher was the urea and urethane hard
segment content, the higher was the glass transition temperature
value and the higher was the elastic modulus of the polyurethane.
On the other hand, the NCO/OH ratio affected the adhesion of the
polyurethanes. In other study [21] it was shown that the mean
particle size of the PUDs decreased but their particle size distributions increased by increasing their solids content. On the other
hand, the increase in the solids content increased the hard segments
content and the degree of phase separation of the polyurethanes.
The greater was the solids content of the polyurethanes, the lower
was their glass transition temperatures values and the lower was
the elastic moduli. Adhesive strength under peel stresses were not
affected by the solids content in the polyurethanes but the single lap-shear strength values decreased by increasing their solid
contents due to lower hard segments content.
Little effort has been paid on synthesizing and characterizing
waterborne polyurethane dispersions prepared with polycarbonate diols of different molecular weight. To the best of our
knowledge, one recent publication by Hwang et al. [23] considered the synthesis and characterization of PUDs synthesized with
polycarbonate diols of different molecular weight. This paper concluded that the average particle size of the PUDs increased with
increasing the molecular weight of polycarbonate diol (from 800 to
2000 Da), because PUDs with higher viscosity and lower ionomer
content were obtained. Furthermore, the mechanical properties of
the polyurethanes prepared from the PUDs increased by increasing
the molecular weight of the polycarbonate diol.
On the other hand, to the best of our knowledge the use of
PUDs as precursors for exible coatings has been scarcely studied although there are some papers dealing with coatings prepared
from PUDs synthesized with other polyols and containing inorganic
particles intended for improving the mechanical and physical properties of the coatings [24,25]. In these papers, polytetramethylene
glycol (Mw = 650 Da) and poly(propylene glycol) (Mw = 400, 500,
600 Da) were used. The PUDs obtained with polytetramethylene
glycol showed higher hardness, tensile strength, rubbery modulus, gel content and swelling resistance, and thermal stability with
respect to the PUDs containing natural clay. The authors concluded
that the chemical interactions between the inorganic and organic
materials played a major role with respect to the particles crowding
in obtaining better properties [24]. On the other hand, the reduction of the molecular weight of poly(propylene glycol) increased
the crosslinking density of the polymer matrix, which results in
restricting the mobility and exibility of the polymer chain [25].
Similarly, Lee et al. [16] found that by increasing the molecular
weight of poly(tetra-methylene adipate glycol), the particle size
and soft segment glass transition temperature of the polyurethane,
Tg , decreased, and the tensile strength was minimal for molecular
weight of 1000 Da. The authors interpreted their results in terms of
soft segment-hard segment phase separation and crystallization of
high molecular weight polyether.
Therefore, in this study the preparation and characterization
of PUDs synthesized with polycarbonates of 1,6-hexanodiol with
different and broader molecular weights (5003000 Da) than in a
previous study [23] to produce polyurethane coatings have been
carried out. The PUDs and the polyurethanes were characterized
and several properties of the polyurethane coatings were studied
including Pencil hardness, Persoz hardness, gloss, yellowness index
and chemical resistance.

1485

Table 1
Nomenclature of the waterborne polyurethane dispersions synthesized with polycarbonate of 1,6-hexanediol of different molecular weight.
Molecular weight of the polycarbonate
of 1,6-hexanediol (Mw) (Da)

Nomenclature
of the PUD

500
1000
2000
3000

PU-U50
PU-U100
PU-U200
PU-U300

2. Experimental
2.1. Materials
The aqueous polyurethane dispersions were prepared by the
acetone process consisting in the reaction of a diisocyanate, a
polyol, an internal emulsier and a chain extender. Polycarbonates
of 1,6-hexanodiol with molecular weights of 500, 1000, 2000 and
3000 Da (supplied by UBE Chemical Europe, Castelln, Spain) were
used as polyols, and they were melted at 70 C for 8 h before use.
The diisocyanate used was isophorone diisocyanate (IPDI,
98 wt% purity) (mixture of cis/trans isomers) (supplied by Aldrich,
Barcelona, Spain). Diethyleneglycol (DEG, 99 wt% purity) and
dimethylolpropionic acid (DMPA, 98 wt% purity) (both supplied
by Aldrich, Barcelona, Spain) were used as short diol and internal
emulsier, respectively, without further purication. Triethylamine (TEA, 99 wt% purity) was used as neutralization agent, and
monohydrated hydrazine (HZ, 99 wt% purity) (both supplied by
Fluka, Madrid, Spain) was used as chain extender. Deionised water
was used as dispersing phase, and high purity acetone (99.5 wt%
purity) was used.
2.2. Synthesis of the waterborne polyurethane dispersions
Four aqueous polyurethane dispersions were prepared with
polycarbonates of 1,6-hexanediol of different molecular weights;
the NCO/OH ratio was 1.5 and their solids content were set to
39 wt%. The DEG content was set to 0.5 wt% and that of DMPA to
5 wt% (both with respect to the prepolymer). The nomenclature
of the waterborne polyurethane dispersions is given in Table 1
and consists in the capital letters PU-U followed by the molecular
weight of the polycarbonate of 1,6-hexanediol.
The polyol, IPDI, DEG and DMPA were added to a glass jacketed reactor equipped with a mechanical stirrer to obtain the
prepolymer. The reaction was carried out at 80 C under nitrogen
atmosphere. When the amount of residual NCO groups reached
the desired value (it was obtained by n-dibutylamine titration),
the prepolymer was dissolved in acetone at 4555 C by continuous stirring at 450 rpm until complete dissolution and then
triethylamine (TEA) aqueous solution was added to neutralize
the carboxylic acid moieties of the DMPA. Afterwards, the chain
extender (hydrazine) was added to complete the reaction with the
unreacted NCO groups. Then, water was added and the mixture
was stirred at 900 rpm for 30 min. Finally, the residual acetone was
removed in a rota vapour unit at 50 C and 300 mbar for 60 min.
2.3. Preparation of the polyurethane lms
Some properties of the polyurethanes were measured in solid
lms that were prepared by placing about 100 cm3 of polyurethane
dispersion in a Teon mould and allowing slow evaporation of the
water at room temperature for 72 h. Afterwards, the remaining
water in the polyurethane was removed by heating at 40 C for 8 h.
Polyurethane lms were about 0.70.9 mm thick.

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2.4. Preparation of the polyurethane coatings

Waterborne polyurethane dispersions were applied on stainless steel no. 304 plates of dimensions 60 mm 50 mm 10 mm
by means of a metering rod of 200 m. The polyurethane coatings
were obtained by drying at room temperature for 72 h. The thickness of the polyurethane coating on stainless steel plate was
measured according to ISO 2808:2007 standard in Neurtek Positector 6000 instrument (Neurtek, Eibar, Spain). The measurements
were carried out at 23 C and 50% relative humidity. The values
obtained were the average of twenty replicates.

carried out in the attenuated total reectance mode by using a ZnSe

prism. An incidence angle of the IR beam of 45 was used, and 100
scans were averaged with a resolution of 4 cm1 .
2.5.2.2. Differential scanning calorimetry (DSC). DSC experiments
were carried out in TA DSC Q100 V6.2. instrument (TA Instruments,
New Castle, Delaware, USA). Aluminium pans containing 1015 mg
of sample were heated from 70 C to 110 C under nitrogen atmosphere (ow rate: 50 ml/min). The heating rate was 10 C/min. The
rst heating run was carried out to remove the thermal history
of the samples. From the second heating run, the glass transition
temperature (Tg ) of the polyurethanes was obtained.

2.5. Experimental techniques

2.5.1. Characterization of the waterborne polyurethane
dispersions (PUDs)
2.5.1.1. pH measurement. About 25 ml PUD was placed in a beaker.
The pH values of the polyurethane aqueous dispersions were measured at 25 C in a pH meter using a silver reference electrode model
HI 8418 (Oakton Instruments, Vernon Hills, Illinois, USA). The pH
was calculated as the average of three experimental determinations.
2.5.1.2. Brookeld viscosity. The viscosities of the PUDs were
measured in Brookeld viscometer LVDV-I-Prime (Brookeld
Engineering Laboratories, Stoughton, MA, USA). About 50 ml waterborne polyurethane dispersion was placed in a beaker and the
measurements were carried out at 25 C by using the spindle no.
61 and the stirring speed of 100 rpm. The Brookeld viscosity was
calculated as the average of three experimental determinations.
2.5.1.3. Solids content. The solids content of the PUDs were
obtained by difference in weight before and after water evaporation. About 1 g PUD was placed on an aluminium container and the
water was evaporated at 105 C in an oven until constant weight
was reached. The solids content was calculated as the average of
three experimental determinations.
2.5.1.4. Particle size. 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 aqueous
polyurethane dispersion was added to a deionised water tank.
The statistical model used to obtain the particle size distribution
assumed that the particles were polystyrene.
2.5.1.5. Transmission electron microscopy (TEM). A Jeol JEM-2310
(Tokyo, Japan) instrument was used to analyze the morphology of
the polyurethane particles in the PUDs; an acceleration voltage of
200 kV was used. To obtain the TEM micrographs of the PUDs, they
were diluted in water and the solutions placed on a copper grid.
2.5.1.6. Drying time. 0.30 g PUD was applied by means of a spatula
on a glass slide of dimensions 25 mm 700 mm. The drying time
was measured according to ASTM D5895-03 standard in BK Drying Time Recorder DT-BK3 (Shean Instruments, Kingston, UK). One
indenter was passing at a constant rate on the top of the wet PUD
lm; once, the PUD is dried, the indenter does not produce any trace
on the PUD lm and the time at which it happened was taken as
the drying time of the PUD.
2.5.2. Characterization of the polyurethane lms
2.5.2.1. Infrared spectroscopy (ATR-IR spectroscopy). The ATR-IR
spectra of the polyurethane lms were obtained in Bruker Tensor
27 spectrometer (Bruker Optik GMbH, Ettlingen, Germany), provided with Fourier transform analysis (FTIR). Measurements were

2.5.2.3. Thermal gravimetric analysis (TGA). TGA experiments were

carried out in TGSD TA thermal balance model 851e/1600/LF (TA
Instruments, New Castle, Delaware, USA). Polyurethane samples
(1015 mg) were heated under nitrogen (ow rate: 100 ml/min)
from room temperature up to 800 C by using a heating rate of
10 C/min.
2.5.2.4. Plateplate rheology. The rheological properties of the
polyurethane lms were determined in shear stress-controlled
Bohlin CS50 rheometer (Optilas Ibrica S.A., Madrid, Spain) using
parallel plates (upper plate diameter = 20 mm); the gap selected
was 0.4 mm. Experiments were performed in the region of linear viscoelasticity by melting the polyurethane lm at 200 C and
cooling down to 30 C at a cooling rate of 5 C/min.
2.5.3. Polyurethane coating properties
2.5.3.1. Hatch adhesion. The adhesion of the polyurethane coatings
was measured according to ISO 2409:2007 standard by using
a multi blade cutting device 0302001 (Sheen Instruments Ltd.,
Surrey, England) and a Scotch adhesive tape. Before test, the
polyurethane coating on stainless steel was kept at 23 C and 50%
relative humidity for 24 h. The values obtained were the average of
three replicates.
2.5.3.2. Pencil hardness. Pencil hardness measures the scratch
resistance of the polyurethane coatings against pencils of different hardnesses. Pencil hardness was measured according ISO
15184:1998 standard in 0300200 Neurtek Pencil hardness instrument (Neurtek, Eibar, Spain). Fig. 1
2.5.3.3. Persoz hardness. Persoz hardness measures the number of
oscillations of a pendulum on a coating surface until it stops, i.e.
the lower is the number of oscillations, the greater is the coating
Persoz hardness. The Persoz hardness of the polyurethane coatings
on stainless steel pieces was measured according to ISO 1522:2006
standard in 707 Konig KP instrument (Shean Instruments, Kingston,
England). The values obtained were the average of three replicates.
2.5.3.4. Gloss. The gloss of the polyurethane coatings on stainless
steel pieces was measured according to ISO 2813:1994 standard
in a Micro-TRI-Gloss instrument (BYK Gardner GmbH, Geretsried,
Germany). Gloss was obtained by directing a constant intensity
light beam at 60 on the coating surface and measuring the reected
light. The values obtained were the average of three replicates.
2.5.3.5. Yellowness index. The yellowness index of the
polyurethane coatings on stainless steel pieces was measured
according to ASTM D1925-70 standard in Minolta CR410 Colorimeter (Minolta, Ramsey, Minnesota, USA). The polyurethane
coating was always maintained into a black box to avoid light
interference in the measurements. The values obtained were the
average of three replicates.

V. Garca-Pacios et al. / Progress in Organic Coatings 76 (2013) 14841493

1487

Fig. 1. Particle size distributions of the waterborne polyurethane dispersions obtained with polycarbonates of 1,6-hexanediol of different molecular weights.

2.5.3.6. Chemical resistance against ethanol. The chemical resistance against ethanol of the polyurethane coatings on stainless steel
pieces was obtained according to ISO 4210:1979 modied standard.
The test consists in applying a fully embedded in ethanol cotton on
the polyurethane coating surface and maintaining it in contact for
different times (10 s to 10 min). The deterioration of the coating
was analyzed according to a scale of 1 (full removal of the coating)
to 5 (intact coating) Table 2.
3. Results and discussion
3.1. Characterization of the waterborne polyurethane dispersions
(PUDs)
The solid contents in the PUDs vary between 35 and 39 wt%
(Table 3). The PUDs have pH values between 7.6 and 8.2 (Table 3),
which are within the range of the commercial and laboratory synthesized PUDs [2022]. Furthermore, the pH of PUDs decreases by
Table 2
Assessment of the chemical resistance against ethanol of the polyurethane coatings
on stainless steel plate (ISO 4210:1979 modied standard).
Code

Extent of damaged surface

5
4
3
2
1

No modication
Change in gloss or colour
Light damage of the coating
Strong damage of the coating
Removal of the coating

increasing the molecular weight of polycarbonate diols likely due

to the lower relative content of urea groups in the polyurethane
(they have Lewis base character). On the other hand, the Brookeld viscosities of the PUDs decrease as the molecular weight of
the polycarbonate of 1,6-hexanediol increases (Table 3) likely due
to the higher length of the hydrocarbon chains in the soft segments
that should facilitate the formation of smaller particles.
Fig. 1 shows the particle size distributions of the aqueous polyurethane dispersions prepared with polycarbonates of
1,6-hexanediol of different molecular weights. All PUDs show
monomodal particle size distribution, except PU-U100 that shows a
bimodal distribution. The particle size of the PUDs decreases as the
molecular weight of the polycarbonate of 1,6-hexanediol increases
(in agreement with Lee et al. [16]) and at the same time the particle
size distribution becomes narrower. The decrease in the particle
size of the PUDs obtained with polyols of high molecular weights
can be ascribed to the decrease in the prepolymer viscosity during
the synthesis that inhibits the fragmentation into smaller particles
during the dispersion in water [7]. This trend is opposite to that
reported by Hwang et al. [23] likely due to the different synthesis
Table 3
Some properties of the waterborne polyurethane dispersions.
Nomenclature

pH

Solids content (wt%)

PU-U50
PU-U100
PU-U200
PU-U300

8.2
8.0
7.9
7.6

35.3
38.8
36.8
38.0

0.3
0.4
0.4
0.1

Brookeld (mPa s)
27.7
26.7
12.8
12.5

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Fig. 2. TEM micrographs of the waterborne polyurethane dispersions obtained with polycarbonates of 1,6-hexanediol of different molecular weights.

procedure used to manufacture the PUDs, but an increase in viscosity by increasing the mean particle size was also found by Hwang
et al. [23]. More recently, for nanosilica-polyurethane composites
obtained from waterborne polyurethane dispersions, Lee et al. [26]
found that the decrease of the dispersion size produced a decrease
in viscosity, in agreement with our results. According the these
authors, the solution viscosity directly contributed to the breakup
of the dispersed phase during phase inversion with water addition
and, assuming stress continuity at interfaces, the smaller dispersed
phase viscosity favoured greater dispersed phase deformation.
TEM micrographs of the PUDs (Fig. 2) conrm that the PUDs
obtained with polycarbonates of 1,6-hexanediol of higher molecular weight have smaller and more homogeneous particle size and
that the particle size increases by decreasing the molecular weight
of the polyol. Furthermore, the particles crowding is favoured in
the PUDs prepared with polycarbonates of 1,6-hexanediol of lower
molecular weight.
In general, the most adequate particle size of the PUD depends
on the specic application to which it is intended. Thus, the PUDs
of relatively larger particles are preferred in surface coatings for
rapid drying whereas the PUDs of smaller particle sizes are desirable when deep penetration of the dispersion into a substrate is
essential [23]. Thus, the particle size of the PUDs should affect the
properties of the coatings obtained from them.
The drying times of the PUDs are short and they vary with
the molecular weight of the polycarbonate of 1,6-hexanediol.
Whereas the PUDs prepared with polycarbonates of 1,6-hexanediol

of molecular weights of 500 and 1000 Da have drying times of

165 min, the ones prepared with polycarbonates of 1,6-hexanediol
of molecular weights of 2000 and 3000 Da have drying times of 120
and 135 min, respectively. The faster drying of the PUDs prepared
with the polyols of higher molecular weight can be related to their
lower mean particle size and narrower particle size distribution.
3.2. Characterization of the polyurethane lms
The chemistry of the polyurethane lms obtained by water
evaporation of the PUDs in a mould was analyzed by ATRIR spectroscopy. ATR-IR spectra of the polyurethanes are
given in Fig. 3a and the assignment of the most characteristic IR bands is given in Table 4. The most characteristic
IR bands correspond to N H stretching at 33373344 cm1 ,
CN stretching and NH stretching at 15301532 cm1 , C H
stretching at 29382340 and 28552861 cm1 , and C O
stretching due to urea (16931697 cm1 ; 16361644 cm1 )
and urethane (17351741 cm1 ) groups. On the other hand,
the ATR-IR spectra show the characteristic C O and N CO O
stretching (12401242 cm1 ; 10341040 cm1 ), and C O C
stretching (11301134 cm1 ; 954963 cm1 ) bands of the
polyol.
The ATR-IR spectra of the polyurethanes prepared with polycarbonates of 1,6-hexanediol of different molecular weights differ
mainly in the chemical structure of the hard segments, i.e. urethane and urea groups (Fig. 3a and b). Thus, according to Fig. 3a,

V. Garca-Pacios et al. / Progress in Organic Coatings 76 (2013) 14841493

1.0
0.5

3337

2855

Absorbance (a.u)

1696
1636

1739

3340

2939

2859

1463

1693
3344

2858

1531

1735
3339

1241

2861

791
902

1242
1130

1532

PU-U300

3000

1036

1460

1695
1644

2938

955

1131

1403

791

1643

1738

PU-U200

1036

1462
1403

1643

960

1133

1530

1697

PU-U100

1.0

0.0

963

1403

1242

2940

0.5

1034

1134

791

0.0
1.0

0.5

1240

1462

PU-U50

1.0
0.5

1531

1741
2936

1489

1400

2000

954

1040

791

1000
-1

Wavenumber (cm )

PU-U50
0.45
0.40

st C=O Urethane (free)

1739
1717

1697

st C=O Urea (free)

0.30

PU-U100
PU-U200

0.25
0.20

(u.a)

Absorbance (a.u.)

0.35

st C=O Urethane (bonded)

PU-U300

st C=O Urea (bonded)

1655

0.15
0.10
0.05

1800

1700

1600

Wavenumber (cm-1)
Fig. 3. (a) ATR-IR spectra of the polyurethanes obtained with polycarbonates of 1,6-hexanediol of different molecular weights. (b) 18501600 cm1 region of the ATR-IR
spectra of the polyurethanes obtained with polycarbonates of 1,6-hexanediol of different molecular weights.

the N H stretching band at 33373344 cm1 becomes relatively

less intense by increasing the molecular weight of the polyol, due
to lower urea content in the hard segments. Furthermore, the
increase in the molecular weight of the polyol decreases the relative intensity of the band corresponding to the bonded urethane
groups (1717 cm1 ), because of the decrease in the hard segment
content in the polyurethane (Fig. 3b). Besides, as urea groups are
created during chain extension of the prepolymer, the increase in
the molecular weight of the polyol decreases the relative intensity of the stretching bands of both free and bonded urea groups
with respect to that of the urethane free groups (16551700 cm1

region) [6,7,19]. Therefore, as the molecular weight of the polycarbonate of 1,6-hexanediol increases, the hard segment content
(urethane and urea groups) in the polyurethanes decreases. Furthermore, the percentage of urethane groups with respect to that
of urea groups increases in the polyurethanes obtained with polyols
of higher molecular weights.
TGA analysis gave information not only about the thermal stability of the polyurethanes but also on their structure, as differentiated
degradation steps of the hard and soft segments can be obtained
[2022]. The thermal stability of the polyurethanes prepared with
polycarbonates of 1,6-hexanediol of different molecular weights

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Table 4
Assignment of the main IR bands in the ATR-IR spectra of the polyurethanes obtained with polycarbonates of 1,6-hexanediol of different molecular weights.
Assignment

st
st
st
st
st

st
st
st
st

N H (bonded)
(asym) C H and st (sym) C H
C O (urethane)
C O (urea)
C N and st N H
CH2
(sym) COO
(asym) N CO O and st C O C
C O C
(sym) N CO O

Wavenumber (cm1 )
PU-U50

PU-U100

PU-U200

PU-U300

3337
2939, 2855
1741
1696, 1636
1531
1462
1403
1240
1134, 963
1034

3340
2939, 2859
1739
1697, 1643
1530
1462
1403
1242
1133, 960
1036

3344
2940, 2858
1738
1693, 1643
1531
1463
1403
1241
1131, 955
1036

3339
2938, 2861
1735
1695, 1644
1532
1460
1400
1242
1130, 954
1040

st, stretching; sym, symmetric stretching; asym, asymmetric stretching.

(Fig. 4) was determined by TGA. In general, the thermal stability

of the polyurethanes increases by increasing the molecular weight
of the polyol as the degradation of thermoplastic polyurethanes
is mainly determined by their soft segments content (it is higher
in the polyols with higher molecular weight). TGA thermograms of
the polyurethanes prepared with polycarbonates of 1,6-hexanediol
of different molecular weights show the main degradations at
310319 C and 343358 C, although other less important degradations can be noticed at lower temperature. Thus, between 55
and 110 C and at 120180 C the removal of residual water in
the polyurethanes is produced, the amount of residual water is
more important in the polyurethane PU-U100, the polyurethane
derived from the only PUD showing bimodal particle size distribution. Because diol and diamine were used in the synthesis of the
polyurethanes, two kind of hard segments are formed, i.e. urethane
and urea. The degradation of the urea and urethane hard segments
can be distinguished in the TGA thermograms at 310319 C. It
has been established [15] that the urethane bond has lower thermal resistance than the urea bond and thus the decomposition
the urethane groups starts earlier. The decomposition of the soft
segments (due to the polyol) is produced at 343358 C (Table 5).
Finally, an additional small degradation at 420 C, likely due to
some residual soft segments, is obtained. The decompositions of
the polyurethanes corresponding to the hard and soft segments
appear at higher temperature and the number of decompositions
increases as the molecular weight of the polycarbonate of 1,6hexanediol increases. On the other hand, according to Table 5 the
weight loss in the polyurethanes corresponding to the soft segments increases as the molecular weight of the polycarbonate of
1,6-hexanediol increases. The different hard and soft segments content in the polyurethanes should affect the coating properties.

Fig. 4. Derivative of the thermal gravimetric (DTGA) thermograms of the

polyurethanes obtained with polycarbonates of 1,6-hexanediol of different molecular weights.

Table 5
Main decompositions in the TGA thermograms of the polyurethanes obtained with
polycarbonates of 1,6-hexanediol of different molecular weights.
PU

Hard segments

PU-U50
PU-U100
PU-U200
PU-U300

Soft segments

T ( C)

Weight loss (%)

T ( C)

Weight loss (%)

310
319
310
319

34
27
23
17

343
351
358
356

13
20
21
30

The inuence of molecular weight of the polycarbonate of 1,6hexanediol on the structure of the polyurethanes was also studied
by differential scanning calorimetry (DSC). The DSC thermograms
of the polyurethanes show two glass transition temperatures (Tg s)
due to the soft segments (Fig. 5). As polycarbonate diol contains
carbonate polar group, the two Tg s can be ascribed to the nonpolar interactions between the hydrocarbon chains in the polyol
(Tg1 ) and to the polar interactions between the carbonate moieties of the polyol (Tg2 ); PU-U100 is an exception. Both the Tg1 and
Tg2 values of the polyurethanes increase as the molecular weight
of the polyol increases (Table 6), that indicates lower degree of
phase separation between the hard and soft segments. On the
other hand, the polyurethanes obtained with polycarbonates of 1,6hexanediol of lower molecular weight show two melting peaks
before decomposition is produced. The increase in the molecular weight of the polycarbonate of 1,6-hexanediol decreases the
rst melting temperature (Tm1 ) of the polyurethanes while the second melting temperature (Tm2 ) increases. Furthermore, the melting
enthalpy is higher in PU-U50. Therefore, the thermal stability of the
polyurethanes increases by increasing the molecular weight of the

Fig. 5. DSC thermograms (glass transition temperature region) of the polyurethanes

obtained with polycarbonates of 1,6-hexanediol of different molecular weights.
Second heating run.

V. Garca-Pacios et al. / Progress in Organic Coatings 76 (2013) 14841493

Table 6
Glass transition temperature, melting temperature and melting enthalpy values
obtained from the second heating run in the DSC curves of the polyurethanes prepared with polycarbonates of 1,6-hexanediol of different molecular weights.

1491

Table 7
Temperature and modulus at the cross-over between the storage and loss modulus
in the polyurethanes obtained with polycarbonates of 1,6-hexanediol of different
molecular weights. Plateplate rheology experiments.

PU

Tg1 ( C)

Tg2 ( C)

Tm1 ( C)

Hm1 (J/g)

Tm2 ( C)

Hm2 (J/g)

PU

Tcross-over ( C)

Gcross-over (Pa)

PU-U50
PU-U100
PU-U200
PU-U300

44

35
40

17
3
43
43

144
139

25
8

156
165

11
3

PU-U50
PU-U100
PU-U200
PU-U300

83
84
79
76

1.1 106
2.9 105
1.3 105
1.4 105

polycarbonate diol. This trend is in agreement with that obtained

with TGA.
The rheological properties of the polyurethanes were determined by plateplate rheology experiments. Fig. 6a shows as
typical example the variation of the storage (G ) and the loss
(G ) moduli as a function of the temperature of the PU-U100
polyurethane. Both moduli of the polyurethane decrease as the
temperature increases, and a cross-over between the storage and
loss modulus is produced. Being viscoelastic, at temperature lower
than that of the cross-over, the elastic regime in the polyurethane
is dominant, whereas at temperature higher than that of the crossover, the viscous regime is dominant. Fig. 6b shows the variation of
the storage modulus (G ) as a function of the temperature for the

polyurethanes synthesized with polycarbonates of 1,6-hexanediol

of different molecular weights. An increase in the molecular weight
of the polyol produces a decrease in the storage modulus (G ), due
to higher soft segment content in the polyurethanes. Similarly,
the cross-over between the moduli shifts towards lower temperature and modulus as the molecular weight of the polycarbonate of
1,6-hexanediol increases (Table 7) due to the increase in the soft
segments content in the polyurethanes.
The storage modulus (G ) can be related to the mechanical properties of the polyurethanes. Therefore, better mechanical properties
can be expected in the polyurethanes synthesized with polycarbonates of 1,6-hexanediol of higher molecular weights. This
assumption is in good agreement with the conclusions of Hwang
et al. [23] as they established that the mechanical properties of the
polyurethanes prepared from PUDs, such as the tensile strength,
increased by increasing the molecular weight of the polycarbonate
diol because the PUDs synthesized with shorter or lower molecular weight polyol had higher reactivity and formed more intensive
polymer networks.
3.3. Coating properties
The thickness of the polyurethane coatings obtained with PUDs
prepared with polycarbonates of 1,6-hexanediol of different molecular weights on stainless steel is 3045 m.
The adhesion of the polyurethane coatings on stainless steel
was evaluated by hatch tests. For polymeric coatings on metal substrates, a good adhesion is required in addition to other functional
properties. Table 8 show the code for assessment of the damaged
polyurethane coating surface after hatch test, i.e. the adhesion of
Table 8
Assessment of the hatch adhesion of the polyurethane coatings (ISO 2409:2007
standard).

Fig. 6. (a) Variation of the storage (G ) and loss (G ) modulus as a function of temperature for the polyurethane PU-U100. (b) Variation of the storage modulus of
the polyurethanes as a function of the molecular weight of the polycarbonate of
1,6-hexanediol.

Code

Description

No modication

Slight loosening of coating (<5%)

Light loosening of the coating (510%)

Partial loosening of the coating (1535%)

Important loosening of the coating (3565%)

Very important loosening of the coating (>65%)

Damaged surface

1492

V. Garca-Pacios et al. / Progress in Organic Coatings 76 (2013) 14841493

Table 9
Pencil hardness values of the polyurethanes obtained with polycarbonates of 1,6hexanediol of different molecular weights.
PU

Pencil hardness (a.u.)

PU-U50
PU-U100
PU-U200
PU-U300

B
4B
6B
6B

the coating on the substrate. The hatch adhesion values of the

polyurethane coatings vary between 0 (polyurethanes synthesized
with polycarbonates of 1,6-hexanediol of low molecular weights,
i.e. 500 and 1000 Da) to 1 (polyurethanes synthesized with polycarbonates of 1,6-hexanediol of higher molecular weights, i.e. 2000
and 3000 Da), indicating excellent adhesion of all polyurethane
coatings to stainless steel plates. Furthermore, the polyurethane
coating adhesion is higher when polyols of lower molecular weight
are used in PUD synthesis likely due to their higher hard segment
contents.
Table 9 shows the variation of the Pencil hardness values of the
polyurethane coatings on stainless steel. The scale of the Pencil
hardness of the coatings was the following one.

Fig. 8. Variation of the gloss (60 ) values of the polyurethane coatings on stainless steel plates as a function of the molecular weight of the polycarbonate of
1,6-hexanediol.

The Pencil hardness of the coatings decreases as the molecular

weight of the polycarbonate of 1,6-hexanediol increases because
of the increase in the soft segments content in the polyurethane.
This is in agreement with previous nding [19] that concluded
that an increase in the hard segments content increased the extent
of cross-linking of the polyurethanes derived from waterborne
polyurethane dispersions.
Fig. 7 shows the variation of the Persoz hardness values of
the polyurethane coatings on stainless steel as a function of the
molecular weight of the polycarbonate of 1,6-hexanediol. The Persoz hardness of the coatings decreases as the molecular weight
of the polycarbonate of 1,6-hexanediol increases because of the
increase in the soft segments content in the polyurethane. This
is in agreement with the results of Pencil hardness. Furthermore,
the extremely high Persoz hardness value in PU-U50 polyurethane
coating can be ascribed to its high stiffness caused by the short
polyol used in its synthesis.

The gloss of the polyurethane coatings on stainless steel

depends slightly on the molecular weight of the polycarbonate
of 1,6-hexanediol above 1000 Da. According to Fig. 8, the gloss
of the polyurethane coatings increases by increasing the molecular weight of the polycarbonate of 1,6-hexanediol from 500 to
1000 Da; however, the gloss of the polyurethane coatings is not
affected when polycarbonates of 1,6-hexanediol of higher molecular weights are used.
Fig. 9 shows the variation of the yellowness index of the
polyurethane coatings on stainless steel. In general, the yellowness index of the coatings increases as the molecular weight of the
polycarbonate of 1,6-hexanediol increases. In general, the higher
soft segment content facilitates the yellowish of the polyurethane
coatings [24].
Finally, the chemical resistance against ethanol of the
polyurethane coatings on stainless steel plates were tested for different times of ethanol in contact with the polyurethane coating
surface. Fig. 10 shows that for short time (10 s or 2 min) of ethanol in
contact with the polyurethane coating surface, the chemical resistance is similar for all polyurethane coatings and it is around 4

Fig. 7. Variation of the Persoz hardness values of the polyurethane coatings on

stainless steel plates as a function of the molecular weight of the polycarbonate
of 1,6-hexanediol.

Fig. 9. Variation of the yellowness index of the polyurethane coatings on stainless steel plates as a function of the molecular weight of the polycarbonate of
1,6-hexanediol.

6B5B4B3B3BBHBFH2H3H4H5H6H

Soft

Hard

V. Garca-Pacios et al. / Progress in Organic Coatings 76 (2013) 14841493

1493

The adhesion of the polyurethane coatings to stainless steel

was very good and decreased slightly by increasing the molecular weight of the polycarbonate of 1,6-hexanediol. Both the Pencil
and Persoz hardness values of the coatings increased by increasing the hard segments in the polyurethane, i.e. by decreasing the
molecular weight of the polycarbonate of 1,6-hexanediol, whereas
the gloss and the yellowness index of the coatings were lower for
the coatings obtained with the polycarbonate of 1,6-hexanediol of
molecular weight of 500 Da. Very good chemical resistance against
ethanol for all polyurethane coating on stainless steel plates was
obtained but for long time of ethanol in contact with the coating
surface the chemical resistance decreased more markedly for the
polyurethane coating obtained with the polycarbonate of 1,6hexanediol of higher molecular weight. Therefore, the segmented
structure of the waterborne polyurethane dispersion and the
polyurethane determined the coating properties.
Acknowledgement
Fig. 10. Variation of the values of the chemical resistance against ethanol of the
polyurethane coatings on stainless steel plates as a function of the molecular weight
of the polycarbonate of 1,6-hexanediol. Values obtained at different times of ethanol
in contact with the coating surfaces (10 s, 2 min and 10 min).

(i.e. good chemical resistance). By increasing the time of ethanol

in contact with the polyurethane coatings to 10 min, the chemical resistance of the polyurethane coatings decreases (mainly in
PU-U300 coating) as the molecular weight of the polycarbonate of
1,6-hexanediol increases, reaching a value as lower as 2 (i.e. strong
damage of the coating). Thus, after 10 min of ethanol in contact
with the polyurethane coating obtained from the PUD prepared
with the polyol of 3000 Da, an important decrease in the chemical
resistance of the coating is produced likely due to its higher soft
segment content.
4. Conclusions
The increase in the molecular weight of the polycarbonate of
1,6-hexanediol (or the increase in the soft segment content in the
polyurethane) decreased the drying time, the mean particle size,
the polydispersity and the Brookeld viscosity of the waterborne
polyurethane dispersions. On the other hand, the decrease in the
molecular weight of the polyol favoured the crowding of the polymer particles, facilitating their collapse and therefore the beginning
of their cross-linking.
The soft segments content in the polyurethanes increased as the
molecular weight of the polycarbonate of 1,6-hexanediol increased.
Because of the decrease in hard segments, the elastic modulus of
the polyurethanes decreased by increasing the molecular weight
of the polycarbonate of 1,6-hexanediol, and the temperature and
modulus at the cross-over between the storage and loss modulus
decreased too. Furthermore, the urethane hard segments became
dominant with respect to that of the urea hard segments in the
polyurethanes prepared with polyols of higher molecular weight.
On the other hand, the increase in the molecular weight of the
polycarbonate of 1,6-hexanediol increased the glass transition temperatures of the polyurethanes, indicating lower degree of phase
separation.

Financial support by UBE Chemical Europe, S.A. is

acknowledged. Contact person at UBE: Dr. Manuel Colera
(m.colera@ube.es).
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