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The waterborne polyurethane dispersions based on polycarbonate diol: Effect

of ionic content

Article  in  Materials Chemistry and Physics · February 2013

DOI: 10.1016/j.matchemphys.2012.11.057

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 Materials Chemistry and Physics 138 (2013) 277e285

Contents lists available at SciVerse ScienceDirect

Materials Chemistry and Physics

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

The waterborne polyurethane dispersions based on polycarbonate diol: Effect of

ionic content
Suzana M. Caki

c a, *, Milena Spírková b
, Ivan S. Risti

c c, Jaroslava K. B-Simendi

c c, Milena M-Cincovi

c d,
Rafa1 Pore˛ ba b
a
University of Nis, Faculty of Technology, Bulevar oslobodjenja 124, 16000 Leskovac, Serbia
b
Institute of Macromolecular Chemistry AS CR v.v.i., Heyrovskeho Nam. 2, 16206 Prague, Czech Republic
c
University of Novi Sad, Faculty of Technology, Bulevar cara Lazara 1, 21000 Novi Sad, Serbia
d
University of Belgrade, Vinca Institute of Nuclear Science, P.O. Box 522, 11001 Belgrade, Serbia

h i g h l i g h t s g r a p h i c a l a b s t r a c t

< Polyurethane dispersions (PUD)

were synthesized from poly-
carbonate diol.
< The effect of the DMPA content on
the thermal properties of PUD films
was measured.
< The thermal stability of PUD was
increased by decreasing the DMPA
content.
< Tg values of PUD were increased by
increasing ionic content.
< The PUD with the highest content of
DMPA showed more significant
phase separation confirmed by AFM
results.

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

Article history: Three water-based polyurethane dispersions (PUD) were synthesized by modified dispersing procedure
Received 26 March 2012 using polycarbonate diol (PCD), isophorone diisocyanate (IPDI), dimethylolpropionic acid (DMPA), trie-
Received in revised form thylamine (TEA) and ethylenediamine (EDA). The ionic group content in the polyurethane-ionomer
4 September 2012
structure was varied by changing the amount of the internal emulsifier, DMPA (4.5, 7.5 and 10 wt.% to
Accepted 18 November 2012
the prepolymer weight). The expected structures of obtained materials were confirmed by FTIR spec-
troscopy. The effect of the DMPA content on the thermal properties of polyurethane films was measured
Keywords:
by TGA, DTA, DSC and DMTA methods. Increased DMPA amounts result in the higher hard segment
Coatings
Chemical synthesis
contents and in the increase of the weight loss corresponding to the degradation of the hard segments.
Thermogravimetric analysis (TGA) The reduction of hard segment content led to the elevated temperature of decomposition and to the
Thermodynamic properties decrease of the glass transition temperature and thermoplasticity. The atomic force microscopy (AFM),
results indicated that phase separation between hard and soft segment of PUD with higher DMPA
content is more significant than of PUD with lower DMPA content. The physico-mechanical properties,
such as hardness, adhesion test and gloss of the dried films were also determined considering the effect
of DMPA content on coating properties.
Ó 2012 Elsevier B.V. All rights reserved.

* Corresponding author. Tel.: þ381 16 247 203; fax: þ381 16 242 859.
E-mail address: [email protected] (S.M. Caki
c).

0254-0584/$ e see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.matchemphys.2012.11.057
278 S.M. Caki
c et al. / Materials Chemistry and Physics 138 (2013) 277e285

1. Introduction the particle size decreased as the ionic group content of the poly-
urethane dispersions increased and their properties were also
Water-based polyurethane dispersions (PUD) have gained affected by the molecular weight of the polycarbonate diols. Vanesa
increasing importance in a range of applications, due to excellent et al. [4,8] studied the effects of different NCO/OH molar ratio on
properties such as adhesion to a wide range of substrates, resis- the properties of waterborne polyurethane dispersions obtained by
tance to chemicals, solvents and water, abrasion resistance and the acetone method.
flexibility [1]. Water-based polyurethane dispersion show very Considering the lack of studies in the existing literature on the
good mechanical and chemical properties and match the regulatory influence of the various ionic content on thermal, mechanical and
pressures for low volatile organic compound (VOC) emission. PUDs dynamicalemechanicalethermal properties, in the present study,
have numbers applications as flexible coatings for textiles and hard water-based polyurethane dispersions derived from isophorone
coatings for wood and metallic surfaces. diisocyanate (IPDI) and polycarbonate diol, were prepared by the
The continuous reduction in costs and the control of VOC modified dispersing method. The ionic groups content in the poly-
emissions increase the use of water-based resins, motivating the urethane structure was varied by changing the amount of the
development of polyurethanes (PUs) dispersed in water. These internal emulsifier-DMPA (4.5, 7.5 and 10 wt.% to the prepolymer
products fulfil many of the requirements related to conventional weight). The aim of this study was investigation of PUDs’ structuree
solvent-born coatings, e.g., low viscosity at high molecular weight properties relationships. The influence of the ionic groups content on
and good applicability. the properties of the polyurethane dispersions was investigated.
The basic components used to obtain PUD include: long-chain According to the analyzed references we have concluded that this is
polyol (polyether, polyester or polycarbonate), diisocyanate the first contribution dealing with the detailed study of the ionic-
(aromatic or (cyclo)aliphatic), low molecular weight glycol and/or content influence on the properties of polyurethane dispersions
amine, bis-hydroxycarboxylic acid and neutralization base. In based solely on polycarbonate diol as the soft segment.
general, an excess of diisocyanate is treated with a linear polyol, bis-
hydroxycarboxylic acid and other low-molecular-weight glycol 2. Experimental
(amine) to form an isocyanate-terminated prepolymer with
a segmented structure. In this polymer, the soft segments are formed 2.1. Materials
from long-chain polyol units and hard segments are built-up from
diisocyanate, glycol (amine) and bis-hydroxycarboxylic acid. Polycarbonate diol T5652 with a molecular weight of 2000,
The polyols used in polyurethane dispersion synthesis are pol- hydroxyl value 56.3 mg KOH/g, was kindly provided by Asahi Kasei
yether-, polyester-, polycaprolactone- and polycarbonate-origin. Corporation. The polycarbonate diol is claimed to be produced from
The use of individual types of polyol chain and their functionality 1,6-hexanediol and 1,5-pentanediol by transesterification with
depends on the purpose of the potential application, e.g.; PU made ethylene carbonate. The molar ratio of 1,5-pentanediol to 1,6-
from polyesters can have slightly elevated strength and oil resis- hexanediol in T5652 is 50:50 and it is liquid at room temperature.
tance compared to polyether-based PUs and have been largely used Isophorone diisocyanate (IPDI) and dimethylolpropionic acid (DMPA)
in polyurethane paints as they exhibit outstanding resistance to were supplied by Aldrich. Ethylenediamine (EDA) was obtained from
light and ageing. Polyether polyols are susceptible to light and Zorka, Serbia; 1-methyl-2-pyrrolidone (NMP), dimethyl formamide
oxygen when hot, however, they improve water dispersion, and (DMF) and triethylamine (TEA) were received from Merk-Schuchardt.
impart chain flexibility [2,3]. The use of polycarbonate diols (PCD) The dibutyltin dilaurate (DBTDL) was supplied by Bayer AG.
in PUs and PUD, as compared to other polyols, imparts better
hydrolysis resistance, improved ageing and oil resistance, excellent 2.2. Synthesis of the waterborne polyurethane dispersions
elastomeric properties even at low temperature, improved
mechanical properties, good weathering and fungi resistance [4]. Three waterborne polyurethane dispersions were prepared by
Polycarbonate diols used as the soft segment component in method in which the dispersing procedure was modified compared
polyurethane synthesis are usually produced from dimethylcar- to standard procedure [9]. For all samples, the NCO/OH molar ratio
bonate or ethylene carbonate and a linear aliphatic diol [5]. The (1.5) was kept constant in formulation. It was defined as a molar
properties of polyurethane dispersions are related to their chemical ratio of IPDI and sum of molar ratio of polycarbonate diol and DMPA
structure [6,7] and they are mainly determined by the interactions in the starting formulation.
between the hard and soft segments, and the interactions between In the standard procedure after obtaining an NCO-terminated
the ionic groups [8]. Recent studies demonstrated that the ionic prepolymer solution, full quantity of water is added immediately
group content, segmented structure, molecular weight of the pol- in order to obtain dispersions with the required solid content. In
yol, the type of chain extender and the hard/soft segment ratio order to eliminate the over-hydrolysis of the NCO groups in the
(NCO/OH) determined PUD properties [8]. The properties of the standard procedure the modified procedure is used.
polyurethane dispersions are strongly influenced by the composi- In the modified procedure only the dispersing stage was varied
tion and ionic content [9,10]. The dimethylolpropionic acid (DMPA) compared to the standard procedure.
containing pendant carboxyl group is one of the most commonly The prepolymer solution was mixed with a small amount of
used hydrophilic ionomer, due to the reactivity of its two OH deionized water for dispersion of polymer in water. Solvent was
groups. The advantage of using this compound is related to the added to reduce the viscosity, if necessary.
steric hindrance of the carboxyl group in compared to tartaric acid The DMPA content was 4.5, 7.5 and 10 wt.% (with respect to the
(TA), so that its interaction with isocyanates is minimized [2]. prepolymer weight), in order to change the ionic-group content in
However, there are still a few studies dealing with the synthesis the polyurethane ionomers.
and characterization of polyurethane dispersions based on poly- Into a 250 ml glass reaction kettle equipped with a mechanical
carbonate diols [4,8e10]. Lee et al. [9] synthesized waterborne stirrer containing a torque meter, a thermometer, a condenser for
polyurethane by using various polycarbonate diol with different reflux and nitrogen gas inlet was added 60 g (0.03 mol) of poly-
molecular weight and the internal emulsifier-dimethylolbutyric carbonate idol (dried under vacuum at 120  C); and 4, 8 or 12 g
acid (DMBA), from 2.4 to 11 wt.% (with respect to the prepolymer (0.03, 0.06 or 0.09 mol) of dimethylolpropionic acid dispersed in
weight), by a modified dispersing procedure. They concluded that 30 ml dimethyl formamide. The reaction mixture was heated at
 S.M. Caki
c et al. / Materials Chemistry and Physics 138 (2013) 277e285 279

Table 1 the total reaction mass) was added and stirred for 1 h to ensure
The compositions of synthesized polyurethane dispersions. complete neutralization the carboxylic acids moieties in the DMPA.
Sample IPDI PCD DMPA TEA EDA Water DMPA/PCD TRS Subsequently, the prepolymer solution was mixed with 0.3 ml of
(g) (g) (g) (g) (g) (g) (mol/mol) (%) deionized water for dispersion step-by-step. Stirring was increased
PUD 1 20 60 4 (4.5)a 3 0.9 204 1.0 30.1 during the addition of water, and the mixture was diluted with NMP.
PUD 2 32 60 8 (7.5) 6 1.8 251 2.0 30.0 Waterborne polyurethane dispersion was obtained by drop-wise
PUD 3 40 60 12 (10) 9 1.8 280 3.0 30.3
addition of enough water to the mixture in order to obtain a poly-
urethane dispersion with solid content of about 30% at 30  C for 1 h.
a
Percentage of DMPA content based on prepolymer weight.
The chain extension was carried with solution of 0.9 or 1.8 g
(0.015 or 0.03 mol) of EDA in 2 ml of deionized water at 35  C for
70  C for 0.5 h to obtain a homogeneous mixture. This step is 1 h. The mixture was heated to 80  C under vacuum in order to
important for the resulting equal uniform distribution of hydro- remove NMP and to obtain a polyurethane dispersion with solid
philic monomer, DMPA, on the polyurethane backbone. After that content of about 30%. The formulations used in the preparation of
20, 32 or 40 g (0.09, 0.15 or 0.18 mol) of isophorone diisocyanate the polyurethane dispersions are summarized in Table 1.
and DBTDL (0.03 wt.% of the total solid) were added to the The reaction scheme for the synthesis of polyurethane disper-
homogenized mixture and stirred at 80  C for 2.5 h. Dibutyl amine sion is illustrated in Scheme 1.
back titration method was used for the determination of the
reaction time necessary to obtain completely NCO-terminated 2.3. Film preparation
prepolymer. Then the mixture was cooled down to 60  C and
stoichiometric amount of TEA (DMPA equiv) (3, 6 or 9 g (0.03, 0.06 Films were prepared by casting the aqueous dispersions on levelled
or 0.09 mol)) dissolved in the 1-methyl-2-pyrrolidone (2 wt.% of glass surfaces and dried at room temperature for 7 days, and then at

Scheme 1. The preparation process for water-based polyurethane dispersion.

280 S.M. Caki
c et al. / Materials Chemistry and Physics 138 (2013) 277e285

Fig. 1. (a) FTIR spectra of the polyurethane ionomer films containing different DMPA content, 3600e1500 cm1 region and (b) details of the 1400e600 cm1 region.

60  C for 12 h [11,12]. Films were casted by 90 mm applicators from the rate of carrier solvent was 1.00 ml min1. Sample injection volume
solutions onto glass surface (7 cm  2 cm) to obtain a dry film thickness was 10 ml. The average molecular masses, Mn, Mw and poly-
of 25e30 mm, making demoulding impossible. After demoulding, the dispersity index Q were determined by software Agilent Chem-
films were kept into the desiccator to prevent absorption of moisture. Station. Poly(methyl metacrylate) standards were used to make
calibration curve.
2.4. Fourier transforms infrared spectroscopy (FTIR)
2.6. TGA analysis
Fourier transform infrared spectra (FTIR): The chemical structure
of the polyurethane ionomers was analyzed in a Michaelson Thermogravimetric analyses (TGA) were performed on the Setaram
Bomem MB-series spectrophotometer, provided with Fourier Setsys Evolution-1750 instrument. Samples (which mass was about
transform analysis (FTIR). Measurements were carried out using 10 mg) were heated from 30  C to 600  C at the heating rate of
the KBr pellet (1 mg/100 mg) technique. 20  C min1 in nitrogen atmosphere with the gas flow rate of
20 cm3 min1. During the heating period, the weight loss and tempera-
2.5. Gel permeation chromatography (GPC) ture difference were recorded as a function of temperature.

The molecular mass distribution of the obtained polyurethane 2.7. Differential scanning calorimetry (DSC)
dispersion films was measured by gel permeation chromatography,
using Agilent 1100 Series system with refractive index. Used Thermal properties of the samples were investigated by differ-
column ZORBAX PSM 300, 250  6.2 mm, 5 mm and operated at ential scanning calorimetry (DSC) using Setaram 151R instrument
temperature 25  C. All samples are dissolved in tetrahydrofuran (software SETSOFT 2000 from Setaram). Hermetically sealed
(THF) of HPLC grade at the constant concentration 0.1wt.%. The flow aluminium pans containing 3e5 mg of sample were prepared. All
 S.M. Caki
c et al. / Materials Chemistry and Physics 138 (2013) 277e285 281

samples were melted at 120  C, to ensure complete melting and Table 2

resetting the thermal history, and rapidly cooled to 60  C. The Characteristic FTIR bands of the polyurethane ionomers [4,13].

non-isothermal measurement was scanned from 60 to 150  C Wavelength (cm1) Assignment
with heating rate 5  C min1. 3460 st NeH (free)
3370 st NeH (bonded)
2.8. Dynamic mechanical thermal analysis (DMTA) 3000e2866 st CeH
2270 st N]C]O
1744 st C]O (free ester and urethane)
The viscoelastic properties of the waterborne polyurethane 1707 st C]O (bonded ester and urethane)
dispersion films were measured on the ARES-LS2 from Rheometrics 1700e1690 st C]O (free urea)
Scientific (now TA instruments). The experiments were carried out 1675e1660 st C]O (bonded disordered urea)
in bending mode (single cantilever) by heating the sample 1640 st C]O (bonded ordered urea)
1610e1550 st asym (COO)
from 100 to 100  C, using a heating rate of 5  C min1, a frequency 1537 st CeN þ d NeH (urea)
of 1 Hz and amplitude of 64 mm peakepeak. 1470e1430 d asym CH3
1475e1450 d CH2
2.9. Atomic force microscopy (AFM) 1406 st sym (COO)
1395e1365 d sym CH3
1248 st asym NeCOeO þ st (CeOeC)
Investigation of the surface topography (height images) and 1131, 955 st (CeOeC)
surface heterogeneities (phase images) of PUD films was performed 1039 st sym NeCOeO þ st (CeOeC)
under ambient conditions using a commercial atomic force st: stretching, d: bending, sym: symmetric, asym: non-symmetric.
microscope (MultiMode Digital Instruments NanoScopeÔ Dimen- Bonded ordered urea: C]O of urea bonded to both NeH groups of a nearby urea
sion IIIa) equipped with the SSS-NCL probe, Super Sharp SiliconÔ e moiety.
SPM-Sensor (NanoSensorsÔ Switzerland); spring constant Bonded disordered urea: C]O of urea bonded to one NH group of a nearby urea
35 Nm1, resonant frequency z 170 kHz. All the measurements
moiety.

were carried using the tapping mode AFM technique. Surface

images were taken from three different film positions in the sizes (1248, 1131 and 955 cm1). The bands at 1248 and 1039 cm1 due
from 1  1 to 40  40 mm2. to asymmetric and symmetric stretching of CeO in the urethane,
split in two for the polyurethane ionomers with lower DMPA
2.10. Polyurethane coatings properties content. The split bands may correspond to the polycarbonate idol,
confirming the higher hard segment content in the polyurethane
The physical and mechanical properties (hardness, gloss, dispersions with higher DMPA content.
adhesion) of resulting product were tested. König pendulum GPC measurements revealed the trend in molecular mass
hardness of cured films determined with a BYK-Gardner pendulum values: The polyurethane ionomer with the highest DMPA (and
hardness tester and the values are reported in seconds (ASTM hard-segment) content shows a slightly higher value than the
D4366). The adhesion performance of the films was tested with others (Table 3). On the other hand, as all PUD samples show very
commercial cello tape according to the cross-cut adhesion test close molecular masses indicating that different DMPA content
method (ASTM D3359). The results are presented using a rating of affect PUD molecular mass only in the limited extent.
0 for a poor adhering coating through 5B for a very good adhering The thermal stability of the polyurethanes was determined by
coating. The gloss characteristics of the films were determined TGA. In according with the literature [4], the decrease of DMPA
according to ASTM D523, with a glossometer “Erichsen gloss- content results in slight increase of the decomposition temperature
master” Model 507, over a resin-coated glass panel at an angle (Fig. 2a) The DTA thermogram of cured films of PUD 1, PUD 2 and
incidence of 60 and reflected light was measured. The final values PUD 3 showed several degradation steps (Fig. 2b and Table 4).
as the average of three measurements were obtained. Thermal stability of PUD is not high, the degradation mecha-
nism is very complex and mainly influenced by the different
3. Results and discussion stability of the hard and soft segment, the nature of the diisocya-
nates as well as content of ionic groups. In literature [4,8,14] it was
FTIR spectroscopy confirmed all anticipated structures in proposed that the thermal degradation of polyurethane disper-
prepared PUD. Fig. 1a shows the comparative FTIR spectra of sions, based on polycarbonate diol, starts at 100e150  C. It repre-
polyurethane dispersions with different DMPA content as hard sents removal of free or hydrogen-bonded water molecules due to
segment content. The assignments of the most characteristic FTIR uncompleted drying of polyurethane film. Due to this phenomena
peaks are given in Table 2. FTIR spectra of samples PUD 1 to PUD 3 the degradation steps are not directly related to the structure of the
feature by the absence of characteristic peak of free NCO groups at analyzed PUD films [14].
2270 cm1, that means the full built-up of IPDI into PU dispersions. In our study, the initial thermal decomposition of polyurethane
The PUD with the increasing of the ionic content in the order dispersions, occurs between 100 and 137  C and it is related with
PUD 1 to PUD 3, slightly increased the intensity of the hydrogen the removal of residual water, adsorbed by the ionic groups. The
bonded NeH stretching band (at 3370 cm1) and CN stretching and DTA thermogram of the used aliphatic polycarbonate diol shows
d NH band of the urea groups at 1537 cm1, because of the increase
in the hard segment content (i.e. the urethane and urea groups). On
the other hand, the decrease in the relative intensity of the free
urethane stretching band at 1744 cm1 with increasing DMPA Table 3
Mean molecular masses and polydispersivity index (Mw/Mn) of the polyurethane
content is accompanied by the increase of relative intensity of ionomers.
stretching bands of the both free and bonded urea groups (1700e
1640 cm1) [13]. Sample Mn Mw Mz Mw/Mn

Fig. 1b shows the detailed CeO region of the FTIR spectra of all PUD 1 3992 4136 4273 1.03
PUD 2 4199 4482 4771 1.07
samples. The NeCOeO stretching band (1039 cm1) corresponding PUD 3 4735 6209 7617 1.28
to urethane and CeOeC stretching bands of the polycarbonate idol
282 S.M. Caki
c et al. / Materials Chemistry and Physics 138 (2013) 277e285

Fig. 2. (a) TG curves and (b) DTA curves of cured films of PUD 1, PUD 2 and PUD 3.

the main degradation at 350  C and other less important at 265  C transition, which is associated with segmental motion in the soft
[4,8]. Because a diol and an ethylenediamine were used in the segments. A peak corresponding to this transition is readily
synthesis of the polyurethanes, two kinds of groups in hard apparent in the tan deT plot follows the same trend with hard
segments have been formed, i.e., urethane and urea ones. The content as does Tg [16].
decomposition temperature of PUD is mostly influenced by the The glass transition is clearly evidenced as maximum in Fig. 3b.
chemical structure of the component having the lowest bond The Tg value of the polyurethane ionomers decreases by increasing
energy [11,15]. The urethane bond has lower thermal resistance the DMPA content. The glass transition temperature of poly-
than the urea bond and thus the first decomposition process at urethanes decreased as their hard segment content increasing has
about 280  C correspond to the beginning of the urethane part of been showed by Garret et al. [17]. The increase in the DMPA content
hard segment degradation and second at about 300  C to the produces a decrease in the crystallinity of the soft segment in the
degradation of the urea part of hard segment. The degradation in polyurethane ionomers, because the decrease in Tg value by
the polyurethanes at 264e268  C is characteristic of the polyol. The increasing the DMPA content can be justified. Figs. 3a and b show
degradation of soft segment (mainly composed of polyol) is a rubbery plateau after the glass transition temperature. The lower
detected at 329e338  C. The soft and hard segments content were the DMPA content induced the greater interactions between the
quantified from the weight loss at above mentioned temperatures soft segments and higher crystallinity of the polyurethane ionomer.
(265  C from PCD degradation, 280  C and 300  C correspond to the Figs. 4aec show the variation of the storage (G0 ) and the loss
urethane and the urea hard segment degradation, and 330  C from 00
(G ) module as a function of the temperature for the polyurethane
degradation of soft segment). ionomer films PUD 1, 2 and 3. The modulus of the polyurethane
According to Table 4, the decrease in the DMPA content ionomers decreased as the temperature increases, and a cross-over
produced a slight increase in the decomposition temperature and between the storage and loss modulus is produced. The cross-over
a decrease in the weight loss for decomposition for urethane and of PUD 1 at e47.6  C, of PUD 2 at e38.8  C and PUD 3 at 37.3  C
urea hard segments, which can be ascribed to a decrease in the moved towards lower temperature as the DMPA content decreases.
amount of hard segment. The decomposition temperature of the Fig. 4d shows decrease in the storage modulus with decrease in the
soft segments is produced at 331e339  C and the weight loss DMPA content [13,18]. The decrease in the DMPA content produces
increases by decreasing DMPA content 20.9 and 23.5 to 6.2 wt.% in polyurethane ionomers with lower resistance to flow under
the polyurethane ionomers [13]. temperature.
The polyurethane ionomer films with different ionic-group The ionic sites in the ionomer interact by coulombic forces and
contents were studied by DMTA. Figs. 3a and b show temperature hydrogen bond and thereby cause interaction between the polymer
dependences of the storage modulus (E0 ) and tan d for samples chains. These ionic groups form aggregates act as physical cross-
PUD1, PUD 2 and PUD 3. links, which are responsible for the increase in the modulus of
In the glassy state, the storage module of all ionomers are of investigated samples. The polyurethane ionomers with higher
108 Pa order, a typical value for polymers in the glassy state. There is DMPA content show higher storage modulus due to mobility
a significant reduction in E0 as the samples pass through the glass decreasing of the ionomer due to their lower soft segment content.
The influence of the DMPA content on the thermal properties of
the polyurethanes was also studied by DSC. The DSC thermograms
Table 4 (Fig. 5) showed only one glass transition temperature. The Tg value
Temperature of decomposition and weight loss of the polyurethane ionomer films
of the polyurethane ionomer increases by increasing DMPA
(TG measurements).
content. As expected, increasing DMPA content i.e., hard segment,
Sample Residual water Soft segment Hard segment leads to an increase in the glass transition temperatures of the
T ( C) Weight T ( C) Weight T ( C) Weight polyurethane ionomer due to restriction of the soft segment
loss loss loss motions by the hard segments [4,13,19]. This trend in Tg is different
(wt.%) (wt.%) (wt.%) than found by DMTA experiments.
PUD 1 130 1.1 268/339 10.1/20.9 282/301 15.5/45.4 The molecular chains of PUD are composed of the soft segment
PUD 2 137 1.0 264/338 3.8/23.5 290/304 20.5/53.7
originating from polycarbonate idol and the hard segment origi-
PUD 3 129 0.9 267/331 10.5/6.2 280/301 22.9/59.3
nating from diisocyanate and ethylenediamine and internal
 S.M. Caki
c et al. / Materials Chemistry and Physics 138 (2013) 277e285 283

Fig. 3. (a) Variation of the storage modulus (E0 ), and (b) tan d as a function of the temperature for the polyurethane ionomer films.

emulsifier. The urethane, urea and carbonate groups in these types hardehard segment by H-bonding with the carbonyl oxygen and
of PUD were able to form hydrogen bonds in which the hydrogen hardesoft segment by H-bonding with the polycarbonate oxygen. If
atom of the NeH group in the urethane linkage donate proton, urea groups are present in the polymer chain, additional types of
while the acceptors can be oxygen atoms of the C]O groups in the hydrogen bonds can be formed. The strength of H-bonding in
urethane or the polycarbonate groups. The NeH group could form hardehard segment is stronger than H-bonding in hardesoft

Fig. 4. Variation of the storage (G0 ) and viscous (G0 0 ) moduli as a function of the temperature for the polyurethane ionomer films (a) PUD1,(b) PUD 2, (c) PUD 3 and (d) variation of
the storage modulus (G0 ) as a function of the temperature for the polyurethane ionomers.
284 S.M. Caki
c et al. / Materials Chemistry and Physics 138 (2013) 277e285

this has resulted in the appearance different intensities of several

bands (Fig. 1).
In this work AFM technique [21,22] was used to study the effect
of the hydrophilic ionomer content on the microphase separation
phenomenon.
Fig. 6 presented the height- and phase-3D AFM image of PUD1
and PUD 3 films. The scope of observation was 20  20 mm2. Typical
two-phase structure can be observed. The comparatively bright
part corresponded to the hard-segment of PUD, and the grey part
corresponded to the soft segment of PUD. If compared height
images for PUD 1 and PUD 3, it is well visible that PU films are very
flat. The individual dispersion particles (or their aggregates) are the
distinct visible on the sample PUD 3. If compared phase images (i.e.,
the sum of tipesample interaction ¼ qualitative information of
local surface heterogeneities) in Fig. 6 samples PUD 1 and PUD 3
have heterogeneity size (nm order) [17,23]. In the 3D image, lots of
part wave trough (soft-segment) and wave crest (hard-segment),
indicate that there was a micro-phase separation in the molecules
of PUD. Furthermore, it can also be seen that with the increase ionic
groups content, the degree of the phase separation was increased.
Fig. 5. DSC thermogram for the polyurethane ionomer films with different DMPA These results are consistent with the phase separation
content.
confirmed by the FTIR method according to Wen et al. [24]. Thus,
obtained results confirm that stronger hardehard segment H-
segment. As the number of interurethane hydrogen bonding is bonding acts as physical cross-links with increasing DMPA content.
higher, the phase of separation is more pronounced [20]. This leads to difficult segmental motion of the polymer chain and in
FTIR analysis of the polyurethanes with different ionic content a more significant phase separation between hard and soft
confirms the phase separation by forming of hydrogen bonds and segments.

Fig. 6. 3D AFM images of micro-phase separation of PUD 1 and PUD 3 films.

 S.M. Caki
c et al. / Materials Chemistry and Physics 138 (2013) 277e285 285

segmented structure of the polyurethanes and a distinction between

soft and hard segments was obtained. The decrease in the DMPA
content produces a decrease in the hard segment content of the
polyurethane ionomers. The thermal stability of the polyurethane
ionomer was increased by decreasing the DMPA content due to the
lower hard segment content. The glass transition temperatures of the
polyurethane ionomer was increased by increasing DMPA content,
due to restriction of the soft segment motions caused by the hard
segments. The PUD with the increasing of ionic groups content
showed the phase separation increased. The increasing of the DMPA
content i.e. hard segment, caused the increasing of König hardness of
the coatings, whereas the gloss of the coatings decreased. Finally, the
cross-over between the storage and loss modulus in the poly-
urethanes shifted towards higher temperature values as the DMPA
content increased, while decrease in the DMPA content produces
polyurethane with lower thermoplasticity.
The effect of different ionic content on the thermal, mechanical
properties and phase separation confirmed by AFM results,
provides an opportunity for a proper selection of fine-tune
performance of waterborne polyurethane dispersions, with
respecting certain practical application. This is a novel approach in
the existing literature that analyse the influence of the ionic
content on the properties of the polyurethane dispersions, based on
polycarbonate diol.

Fig. 7. 2D AFM height image of sample PUD 3. Acknowledgements

The project was financed by the Ministry of Science and Tech-

Table 5 nological Development of the Republic of Serbia (Projects No. III
Physical and mechanical properties of polyurethane ionomer films.
45022 and III 45020) and the Grant Agency of the Czech Republic
Sample Hardness (s) Gloss (%) Adhesion (Czech Science Foundation, project No. P108/10/0195).
PUD 1 32.2 147.6 5B
PUD 2 51.0 122.7 5B References
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