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Progress in Organic Coatings 75 (2012) 579583

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Progress in Organic Coatings
j our nal homepage: www. el sevi er . com/ l ocat e/ por gcoat
Synthesis and characterization of transparent and high impact resistance
polyurethane coatings based on polyester polyols and isocyanate trimers
Junrui Zhang
a,b
, Weiping Tu
a,
, Zilin Dai
b
a
School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, China
b
Institute of Chemical Engineering, Guangdong General Research Institute of Industrial Technology, Guangzhou 510651, China
a r t i c l e i n f o
Article history:
Received 5 January 2012
Received in revised form21 March 2012
Accepted 12 May 2012
Available online 11 July 2012
Keywords:
Polyester polyols
Polyurethane
Impact resistance
Transmittance
a b s t r a c t
A series of polyester polyols were synthesized by polycondensation reaction using adipic acid (AA), 1,4-
cyclohexanedicarboxylic acid (1,4-CHDA), and 1,6-hexanediol (HDO), 1,4-cyclohexanedimethanol (1,4-
CHDM) and trimethylol propane (TMP), in which the molar ratio of the reactants AA/1,4-CHDA was
varied. These series of polyols were reacted with isophorone diisocyanate (IPDI) and hexamethylene
diisocyanate (HDI), alone or in combination, to form polyurethane (PU) coatings.
The physicochemical properties (chemical structure, hydroxyl value, acid value, and molecular weight)
of the polyols so synthesized and the mechanical and optical properties (impact resistance, lm exibility,
optical transmittance and phase separation) of the PU coatings so prepared were characterized with FTIR
spectroscopy, wide angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC) and atomic
force microscopy (AFM).
The results of this study show that the AA/1,4-CHDA molar ratio, the isocyanate used, and the NCO/OH
ratio all have a signicant impact on the properties of the PU coatings. While AA/1,4-CHDA molar ratio
does not seem to affect the lm exibility and optical transmittance of the PU coatings, it has a signicant
effect on the impact resistance of the coatings. Impact resistance of the PU coatings increases as the
AA/1,4-CHDA molar ratio decreases (i.e. more 1,4-CHDA used). PU coatings based onIPDI and combination
of IPDI and HDI exhibit higher impact resistance and optical transmittance than HDI-based coatings.
While changing NCO/OH ratio has only a slight impact on the optical transmittance and little effect on
lm exibility, impact resistance of the PU coatings rst increase, then decline with an increase inNCO/OH
ratio.
2012 Published by Elsevier B.V.
1. Introduction
Polyurethanes (PUs) are used in the manufacture of wide vari-
ety of industrial and consumer products, which in large part is
attributed to the fact that they possess several attractive mechan-
ical and chemical properties [13]. They exhibit excellent tensile
strength, high resilience and wear resistance, as well as high
exibility even at lowtemperatures. They are also capable of with-
standing corrosive or chemically adverse environment.
While coatings made from polyurethanes inherit many of the
unique properties of the bulk materials, thus enabling them to be
widely used as well, conventional PU coatings suffer from some
serious application drawbacks, however. These include insufcient
impact resistance, and propensity to UV degradation when used
in an outdoor environment [48]. There have been reports [911]
of novel synthetic routes and processes to produce PU coatings

Corresponding author. Tel.: +86 20 87113486; fax: +86 20 87113486.


E-mail address: cewptu@scut.edu.cn (W. Tu).
of improved mechanical and chemical properties, in attempts to
strengthen the application performance of PU coatings.
Hydroxylated polyesters (HPEs) are the most common polyols
used for making two-pack PU coatings, and the properties of the
diacids used in preparing the HPEs have serious implications for
the performance of the PU coatings. It has been observed [12] that
HPEs made fromaromatic diacids produce PUcoatings of increased
hardness and chemical resistance as well as higher glass tran-
sition temperature (Tg). However, the phenyl rings contained in
the aromatic diacids absorb UV-light, resulting in photo-oxidative
degradation and yellowing of PU coatings made fromthese diacids
upon outdoor exposure.
Diisocyanates are the other important starting materials for
the manufacture of PU coatings. Trimers of aliphatic and alicyclic
diisocyanate are less toxic and impart better thermal stability and
enhanced mechanical properties to the PUcoatings [9,13,14]. Thus,
they are usually used in high-grade weather-resistance coatings.
The present study describes the synthesis of a series of polyester
polyols by polycondensation reaction using adipic acid (AA),
1,4-cyclohexanedicarboxylic acid (1,4-CHDA), and 1,6-hexanediol
0300-9440/$ see front matter 2012 Published by Elsevier B.V.
http://dx.doi.org/10.1016/j.porgcoat.2012.05.005
580 J. Zhang et al. / Progress in Organic Coatings 75 (2012) 579583
Table 1
The formulations and designations of polyester polyols.
Sample n(AA)/n(1,4-CHDA) HDO (mol) 1,4-CHDM(mol) TMP (mol) n(OH)/n(COOH)
1 9:1
0.475 0.16 0.032 1.4:1
2 7:3
3 5:5
4 3:7
5 1:9
6 0:10
(HDO), 1,4-cyclohexane dimethanol (1,4-CHDM) and trimethy-
lol propane (TMP), in which the molar ratio of the reactants
AA/1,4-CHDAwas varied. These series of polyols were reacted with
isophorone diisocyanate (IPDI) and hexamethylene diisocyanate
(HDI), alone or in combination, to formpolyurethane (PU) coatings.
The physicochemical properties (chemical structure, hydroxyl
value, acid value, and molecular weight) of the polyols so syn-
thesized and the mechanical and optical properties (impact
resistance, lm exibility, optical transmittance and phase
separation) of the PU coatings so prepared were charac-
terized with FTIR spectroscopy, wide angle X-ray diffraction
(WAXD), differential scanning calorimetry (DSC) and atomic force
microscopy (AFM).
2. Materials and methods
2.1. Materials
1,4-cyclohexanedicarboxylic acid (1,4-CHDA) and 1,4-
cyclohexanedimethanol (1,4-CHDM) were obtained from SK
Chemicals (Korea). Adipic acid (AA), trimethylol propane (TMP)
and 1,6-hexanediol (HDO) were purchased from Alfa Aesar (USA).
Isophorone diisocyanate (IPDI) trimer (Desmodur Z4470) and
hexamethylene diisocyanate (HDI) trimer (Desmodur N3390)
were supplied by Bayer Corporation (Germany). BYK306 (BYK
Chemie; Germany) was used as leveling agent. All other reagents
were of analytical grade.
2.2. Synthesis of polyester polyols
A series of polyester polyols were synthesized by polyconden-
sation reaction using AA, 1,4-CHDA, and HDO, 1,4-CHDMand TMP
in a composition shown in Table 1. Varying the molar ratio of
the two diacids used but maintaining a xed diacid/diol molar
ratio, a total of 6 polyester polyols were synthesized (Table 1).
The polycondensation reactions were performed in a 250mL reac-
tor equipped with mechanical stirrer, nitrogen purging device and
Dean-Stark trap used for separating water and xylene. The reaction
mixturewas stirredcontinuously, whilemaintainingthemaximum
temperature at the post stage at 210

C, until the polyester resin


reached an acid number between 1 and 3 (mg KOH/g resin). The
acidnumber andhydroxyl number of thepolyesters weremeasured
according to the ASTM Methods D1639-90 and D1957-09 [15,16],
respectively.
2.3. Preparation of PUs and PU coatings
PUs were prepared by mixing the polyesters with isocyanate
trimers in an appropriate solvent system. Polyesters obtained from
the polycondensation reactions described above were diluted in a
mixed solvent of cyclohexanone (CYC) and butyl acetate (BAC) (in
a mass ratio of CYC: BAC=2:1) and then mixed with trimers of IPDI
and/or HDI in the presence of a leveling agent (0.1wt% of reactants
andsolvent). Thesolidcontent of thesystemwas kept at 4041wt%.
PU coatings were prepared by casting the PU solutions onto
iron plates which had been degreased with acetone. The cast PU
lms were maintained at a thickness of 0.20.3mm by a draw-
bar, and were cured at 80

C for 24h. The cured lms were kept


under ambient atmospheric conditions for 2 days before testing
and characterization were performed.
2.4. Testing methods
Gel permeation chromatography (GPC) was used to determine
the molecular weight and molecular weight distribution of polyols.
GPC analysis was carried out on Perkin Elmer Series-200 using PL
gel (10m) 300mm7.5mm mixed-B columns. The calibration
curve was obtained with polystyrene standards. Tetrahydrofu-
ran (THF) was used as mobile phase and delivered at a rate of
1.0mL/min.
Reverse impact resistance and exibility were performed
according to GB/T 1732-93 [17], GB/T 1731-93 [18]. Water resis-
tance was characterized according to GB/T1733-93 [19]. The static
contact angles of water droplets on the PUlmsurfaces were mea-
sured with a Dataphysics OCA40 Micro. 1L of water was dropped
onto the PU coating surface using a syringe, and a camera with
the aid of a magnifying lens captured the prole of the droplet
immediately.
Optical transmittance of the PU lms were characterized by a
WGW apparatus, which is designed and made according to the
ASTM Method D1033-61 (1977) and UVVIS spectrophotometer
(Hitachi U-3010, Japan).
Wide Angle X-ray diffraction (WAXD) patterns were obtained
on Bruker-D8 ADVANCE at room temperature (Cu radiation,
40kV/40mA). Angel 2 was scanned from 3

to 40

with the step


size of 0.02

(2) and 17.7s/step.


Differential scanning calorimetric (DSC) thermograms were
obtained with DSC (NETZSCH DSC 204) in the temperature rage
of 60 to 350

C with a heating and cooling rate of 10

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

C. The water absorptionwas less than5%after the coatings were


dipped in distilled water for 16 days. These results indicate that the
PU coatings were properly cross-linked, enabling them withstand
adverse outdoor environment [21].
3.5. AFManalysis of PU coating
Phase image and 3Dimage of PUcoating are shown in Fig. 5. The
phase image showeda relativelysmall-scale phase separation, with
aseparationdegreeof 0.147. Inthephaseimageandthe3Dimageof
the coating, the bright regioncorresponds to the hardsegment-rich
phase while the dark region is associated with the soft segment-
rich phase [22]. It should be noted that it is the small-scale phase
separation that imparts PU coating its excellent performances.
Fig. 4. Contact angle analysis of PU coating (polyols(1:9), m(Z4470)/m(N3390)
= 2:1,NCO/OH=1.2).
J. Zhang et al. / Progress in Organic Coatings 75 (2012) 579583 583
Fig. 5. Phase image and 3D image of PU coating based on AFM (polyols(1:9),
m(Z4470)/m(N3390) =2:1,NCO/OH=1.2)
4. Conclusion
A series of polyester polyols were synthesized by polyconden-
sation reaction using adipic acid (AA), 1,4-cyclohexanedicarboxylic
acid (1,4-CHDA), and 1,6-hexanediol (HDO), 1,4-cyclohexane
dimethanol (1,4-CHDM) and trimethylol propane (TMP), in which
the molar ratio of the reactants AA/1,4-CHDA was varied. These
series of polyols were reacted with isophorone diisocyanate (IPDI)
and hexamethylene diisocyanate (HDI), alone or in combination, to
formpolyurethane (PU) coatings.
The physicochemical properties (chemical structure, hydroxyl
value, acid value, and molecular weight) of the polyols so
synthesized and the mechanical and optical properties (impact
resistance, lm exibility, optical transmittance and phase sepa-
ration) of the PU coatings so prepared were characterized with
FTIR spectroscopy, wide angle X-ray diffraction (WAXD), differ-
ential scanning calorimetry (DSC) and atomic force microscopy
(AFM).
The results of this study showthat the AA/1,4-CHDAmolar ratio,
the isocyanate used, and the NCO/OH ratio all have a signicant
impact on the properties of the PU coatings. While AA/1,4-CHDA
molar ratio does not seem to affect the lm exibility and opti-
cal transmittance of the PU coatings, it have a signicant effect
on the impact resistance of the coatings. Impact resistance of the
PU coatings increases as the AA/1,4-CHDA molar ratio decreases
(i.e. more 1,4-CHDA used). PU coatings based on IPDI and com-
bination of IPDI and HDI exhibit higher impact resistance and
optical transmittance than HDI-based coatings. While changing
NCO/OH ratio has only a slight impact on the optical transmit-
tance and little effect on lm exibility, impact resistance of the
PUcoatings rst increase, then decline with an increase in NCO/OH
ratio.
Acknowledgement
This workwas supportedbyagrant fromtheResearchInitiatives
of Guangdong Province, China (grant no. 2010A09020025).
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