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to 40
C/min under
nitrogen atmosphere. The data captured was that of the second
heating run to reduce the thermal history of the samples.
Surface morphology of PU coatings were recorded on an AFM
(SEIKO SPI3800N) operated at room temperature and in tapping
mode, using Si
3
N
4
probe.
3. Results and discussion
3.1. Characterization and properties of polyester polyols and PU
coatings
The properties of polyester polyols prepared in this study are
listed in Table 2. Molecular weights were controlled by hydroxyl
number which was determined through titration. All polyester
polyols prepared in this study were transparent liquids at room
temperature.
The FTIR spectral data of polyester polyols and PUs are shown
in Table 3. Broad band from 3540 to 3400cm
1
is a characteristic
band of OH stretching vibrations. Single band at 1727cm
1
is
the characteristic stretching band of carbonyl group of polyester
polyols. Absorption at 1175cm
1
is for C O group of polyester
compound. Stretching vibration of (CH
2
)n shows absorption at
756cm
1
. C H stretching is at 1457 and 1383cm
1
. The bands at
J. Zhang et al. / Progress in Organic Coatings 75 (2012) 579583 581
Table 2
The properties of polyester polyols as a function of difunctional acids.
Sample n(AA)/n(1,4-CHDA) Acid value (mgKOH/g) Hydroxyl value (mgKOH/g) Mn (g/mol) PDI
1 9:1 1.54 106.8 3284 1.30
2 7:3 1.3 105.7 2999 1.23
3 5:5 1.12 98.3 3093 1.26
4 3:7 1.5 92.6 3036 1.24
5 1:9 1.5 86.1 3127 1.27
6 0:10 1.37 93.8 3066 1.25
Table 3
FTIR spectral assignment of polyester polyols and PU coatings.
Functional group Wave numbers(cm)
Polyester polyols Polyurethanes
OH str. 35403400 (broad band)
>C O str. (polyesters) 1727 1684
CH2 str. sym. 2838 2827
CH2 str. asym. 2938 2927
C H bending 1457,1383 1465,1391
C O str. (polyesters) 1175 1236
C O C str. (polyesters) 1038 1036
(CH2)n- str.(polyesters) 756 768
NH (urethane) 3380
N H deformation 1521
>C O (urethane) 1724
2938and2838cm
1
are due toasymmetric andsymmetric stretch-
ing of CH
2
. The FTIR data are consistent with that of a polyester
polyol structure, indicating that what were obtained in the poly-
condensationreactions were indeed polyester polyols. FTIRspectra
of polyester in PU showed a little shift because of electronic effect
or hydrogen bond, and PU coatings showed additional characteris-
tic bands at 1724and3380cm
1
corresponding tocarbonyl ( C O)
and amide ( NH) stretchings in urethane, respectively. Single band
at 1684cm
1
are the characteristic stretching band of carbonyl
group of polyester polyols in PUs. The bands at 1521cm
1
are char-
acteristic of N-H deformation. The absence of the characteristic
stretching band of N C O at 22502300cm
1
indicates that the
coatings had all been cured.
3.2. Effect of isocyanates and NCO/OH ratio on PU coating
properties
There have been reports [9,20] that PU coatings prepared from
isocyanate trimers exhibit improved weather resistance attributes,
mechanical properties and thermal stability. In this study, trimers
of IPDI and HDI alone or in combination were employed in prepar-
ing PUs. Impact resistance, lmexibilityandoptical transmittance
were characterized of PUcoatings prepared froma polyester polyol
synthesized using AA and 1,4-CHDA at a xed molar ration of 7:3
(AA: 1,4-CHDA). Thetrimers usedinpreparingthePUcoatings were
variedfromZ4470or N3390alone or incombination(whenincom-
bination, use the xedmass ratioof Z4470:N3390=2:1), but always
maintaining a xed OH/NCO ratio of 1:1.2. Table 4 and Figs. 13
summarize the characterization results of these PU coatings. As
can been seen from these results, these coatings all had excellent
lm exibility, optical and impact resistance properties. All these
Table 4
Effect of isocyanates on the properties of PU coatings.
Isocyanates Impact
resistance
(kgcm)
Flexibility (mm) Transmittance (%) Haze (%)
IPDI 70 1 93.8 14.8
HDI 60 1 82.4 14.3
IPDI +HDI 75 1 87.4 13.6
45 40 35 30 25 20 15 10 5 0
0
200
400
600
800
1000
1200
B
D
F
I
n
t
e
n
s
i
t
y
2
B--N3390
D--Z4470
F--m(Z4470):m(N3390)=2:1
Fig. 1. X-ray diffraction spectrumof PU coatings based on different isocyanates.
300 250 200 150 100 50 0 -50
-0.30
-0.25
-0.20
-0.15
-0.10
-0.05
0.00
0.05
0.10
0.15
0.20
e
x
o
Temperature
Z4470
m(Z4470):m(N3390)=2:1
N3390
Fig. 2. DSC curves of PU coatings based on different isocyanates.
700 600 500 400 300 200
0
20
40
60
80
100
T
r
a
n
s
m
e
t
t
a
n
c
e
Wavelength, nm
N3390
Z4470
m(Z4470):m(N3390)=2:1
Fig. 3. Effect of isocyanates on transmittance of PU coatings.
582 J. Zhang et al. / Progress in Organic Coatings 75 (2012) 579583
Table 5
Effect of NCO/OH ratio on the properties of PU coatings.
NCO/OH ratio Impact
resistance
(kgcm)
Flexibility
(mm)
Transmittance (%) Haze (%)
0.8 60 1 91.8 18.1
1.0 65 1 89.0 15.5
1.2 75 1 87.4 13.6
1.4 70 1 87.0 14.9
1.6 65 1 87.3 11.8
coatings exhibited some degree of haze, which is probably caused
by light scattering fromthe interior or surface of the coatings.
PU coatings based on IPDI showed higher impact resistance,
indicating improvedelasticity of the lms, whichmay be attributed
to the asymmetry structure of the molecule. HDI has a symmet-
rical structure, which makes HDI-based coating easily crystallize,
thus lowering its elasticity and optical transparency. Adding IPDI
to HDI destroys the crystalline structure of HDI-based PU coating
and improves its elasticity and optical properties. This interpreta-
tion of results is consistent with the X-ray diffraction data (Fig. 1),
which shows a sharp peak in the region of 2 =20
for HDI-based
coating, indicating a distinct crystalline structure. Incontrast, inthe
same region of the X-ray diffraction pattern, only a broad peak with
much lower intensity was observed for the IPDI and (IPDI +HDI)-
based coatings, indicating a far less crystalline structure. The X-ray
diffraction data were further conrmed by a DSC study of the 3
different PU coatings (Fig. 2). As can be seen, the soft segment
had no obvious exothermic peak, while the hard segment had a
slight exothermic peak, conrming that crystallization was caused
by the hard segment. Crystallization reduced the transparency of
the polyurethane lm, which can be seen fromFig. 3.
Effect of NCO/OH ratio on the properties of PU coatings is
shown in Table 5. PU coatings prepared from a polyester polyol
synthesized using AA and 1,4-CHDA at a xed molar ration of
7:3 (AA: 1,4-CHDA). The trimers used in preparing the PU coat-
ings were combination of Z4470 or N3390 (the xed mass ratio
of Z4470:N3390=2:1). As can be seen from the results, changing
NCO/OH ratio has a slight impact on the optical transmittance and
little effect onlmexibility. However, withanincrease inNCO/OH
ratio, impact resistance of the coatings rst increase, then decline.
This may be a result of low cross-linking in the lms at a low
NCO/OH ratio as there are no enough NCO groups to react with
all OH groups present, leading to low impact resistance. However,
as the NCO/OH ratio increases and goes beyond a certain value,
urea groups would be increasingly generated, resulting in a decline
in impact resistance. The results in Table 5 also show that all PU
coatings prepared in a series of NCO/OH ratios exhibited high lm
exibility and excellent optical transmittance, which may indicate
lowcrystallization of both soft and hard segments of the PUs.
3.3. Effect of AA/1,4-CHDA molar ratio on the properties of PU
coatings
PUs consist of alternating soft and hard segments. They have
different degree of micro separation structures because of the
thermodynamics incompatibility of soft and hard segments in the
polymers. Effect of AA/1,4-CHDA molar ratio on the properties of
PU coatings are shown in Table 6. The polyurethanes based on a
series of AA/1,4-CHDA molar ratio (respectively, 9:1, 7:3, 5:5, 3:7,
1:9 and 0:10) all have similar exibility and optical transmittance
properties. However, a remarkable difference in impact resistance
were observed with the series: impact resistance of the PU coat-
ings increases as the AA/1,4-CHDA molar ratio decreases (i.e. more
1,4-CHDA used), and it declines only slightly when 1,4-CHDA
alone was used. The long linear structure in adipic acid imparts
Table 6
AA/1,4-CHDA molar ratio on the properties of PU coatings (m(Z4470)/m(N3390)
= 2:1, NCO/OH=1.2).
n(AA)/n(1,4-CHDA) Impact
resistance
(kgcm)
Flexibility
(mm)
Transmittance
(%)
Haze (%)
9:1 70 1 89.1 9.0
7:3 75 1 87.4 34
5:5 80 1 89.8 34.2
3:7 85 1 89.1 35.4
1:9 100 1 88 30
0:10 90 1 89.5 48
polyurethane coatings with high elasticity as it has weaker inter-
molecular force, while the cyclic structure in 1,4-CHDA improve
the rigidity of the coatings. Hence, polyurethanes made completely
fromcycloaliphatic diacids exhibit higher hardness but lower elas-
ticity.
3.4. Water resistance
Contact angle measurement of PU coatings is shown in Fig. 4.
Water absorptionwas detectedaccordingtoGB/T1733-93. Thesur-
face of PUcoatings was hydrophobic as the contact angle was above
90