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Contents lists available at ScienceDirect

Progress in Organic Coatings

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

Synthesis of HDI/IPDI hybrid isocyanurate and its application in

polyurethane coating
Guiyou Wang a,∗ , Kang Li a , Wei Zou a , Aiguo Hu a , Chunpu Hu a , Yangping Zhu b ,
Chen Chen b , Glynn Guo b , Aaron Yang b , Ray Drumright c , John Argyropoulos c
a
Shanghai Key Laboratory of Advanced Polymeric Materials, School of Materials Science and Engineering, East China University of Science and Technology,
Shanghai 200237, China
b
Dow Chemical Company Limited, No. 936, Zhang Heng Road, Zhangjiang Hi-Tech Park, Shanghai 201203, China
c
The Dow Chemical Company, Midland, MI 48674, USA

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

Article history: A solvent-free hybrid isocyanurate was prepared by trimerization of hexamethylene diisocyanate (HDI)
Received 2 April 2014 and isophorone diisocyanate (IPDI), and characterized by gel permeation chromatography (GPC), gas
Received in revised form 20 June 2014 chromatography (GC), nuclear magnetic resonance (NMR), and electrospray ionization mass spectrome-
Accepted 25 August 2014
try (ESI-MS). The results showed that HDI/IPDI hybrid isocyanurate could be prepared in the presence of
Available online xxx
2-hydroxypropyl-trimethyl-azanium catalyst at reaction temperatures between 50 ◦ C and 70 ◦ C. Both the
GC and 1 H NMR analyses identified the favorable linear relationship between the feed ratio of the start-
Keywords:
ing monomers and the amount of each individual isocyanate incorporated into the oligomer (reaction
Isophorone diisocyanate
Hexamethylene diisocyanate
ratio). The polyurethane coatings prepared with HDI/IPDI hybrid isocyanurates demonstrated faster dry-
Coating ing speed, higher hardness and gloss and better distinctness-of-image (DOI) than the analogous coatings
Hybrid isocyanurate prepared with cold-blends of HDI isocyanurate and IPDI isocyanurate.
Polyurethane © 2014 Elsevier B.V. All rights reserved.
Structure

1. Introduction isocyanurate and IPDI isocyanurate is commonly practiced in the

For high-quality one- and two-component polyurethane coating
materials, the isocyanate component employed is an isocyanurate.
Isocyanurates are prepared by cyclic trimerization of isocyanates
and are well known [1–5]. Coatings based on isocyanurates derived
from aliphatic isocyanates exhibit excellent light and weather
stability and as a consequence are principally used for outdoor
application [6–8]. The two main commercial aliphatic isocyanu-
rates are based on HDI and IPDI, and are useful as components
of formulations for various coatings applications (e.g., automotive
coatings and architectural paints) [9].
Polyurethane coatings prepared from IPDI isocyanurate have the
advantage of quick drying and high hardness. However, IPDI isocya-
nurate requires solvent for handling and formulation. In response
to consumer preference and increasingly-tightening governmental
regulation on the presence of volatile organic compounds (VOCs),
low viscosity polyisocyanates are desirable [10]. HDI isocyanurate
is very suitable for this purpose. Blending HDI isocyanurate with
IPDI isocyanurate not only decreases the viscosity but also yields
polyurethane coatings with higher gloss. As such, blending of HDI
∗ Corresponding author. Tel.: +86 2164252271; fax: +86 2164252271.
E-mail address: guiyouwang@ecust.edu.cn (G. Wang).
automotive coating industry. However, heterogeneity in the coat-
ing surface resulting in low DOI (distinctness of image) arising from
the different reactivities of HDI isocyanurate and IPDI isocyanurate,
create formulation and application difficulties.
In this paper, the hybrid isocyanurate of HDI/IPDI was pre-
pared in an attempt to overcome the aforementioned problems. The
structure of hybrid isocyanurate was confirmed. The relationship
between the feed ratio of the starting monomers and the amount
of each individual isocyanate incorporated into the isocyanurate
oligomer (reaction ratio) was determined. In addition, the relation-
ship between the distribution of isocyanurate oligomers and the
reaction conversion was elucidated. Finally, the physical properties
of the polyurethane coatings prepared from HDI/IPDI hybrid isocya-
nurate and cold blend of HDI isocyanurate and IPDI isocyanurate
were compared.
2. Experiment
2.1. Materials
HDI monomer, industrial grade, was supplied from Bayer AG.
IPDI monomer, industrial grade, was supplied from Bayer AG. Dabco
TMR (2-hydroxypropyl-trimethyl-azanium) was produced by Air
Products and Chemicals, Inc. Benzoyl chloride, CP, was produced by

http://dx.doi.org/10.1016/j.porgcoat.2014.08.017
0300-9440/© 2014 Elsevier B.V. All rights reserved.

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Shanghai LingFeng Chemical Reagent Co., Ltd. n-tetradecane, chro-
matographic pure, was supplied from Acros Organics. Desmophen
A365 BA/X, a hydroxyl-functional polyacrylate resin, glass transi-
tion temperature (Tg ): about 8 ◦ C, equivalent weight: about 585,
hydroxyl content: about 2.9%, non-volatile: about 65% in butyl
acetate/xylene (3:1), was supplied from Bayer AG. Desmophen
A870 BA, a hydroxyl-functional polyacrylate resin, Tg : about −15 ◦ C,
equivalent weight: about 575, hydroxyl content: about 2.95%, non-
volatile: about 70% in butyl acetate, was supplied from Bayer AG.
Hypomer FX-2460AF, a hydroxyl-functional polyacrylate resin, Tg :
about 60 ◦ C, hydroxyl content: about 1.44%, non-volatile: about
62% in butyl acetate/propylene glycol monoethyl ether acetate,
was supplied from Elementis Co., Ltd. Desmodur N3300, pure HDI
trimer, NCO content: 21.8%, was supplied from Bayer AG. Desmodur
Z4470 BA, pure IPDI trimer, NCO content: 11.9%, solids content: 70%
in butyl acetate, was supplied from Bayer AG. Other materials were
standard laboratory reagents and were used as received.
2.2. Synthesis of HDI/IPDI hybrid-isocyanurate
All the reactions were carried out in a 100 mL three-neck flask in
an oil bath, which was equipped with a mechanical stirrer, an argon
inlet, and a thermometer. In the first step, a calculated quantity of
HDI, IPDI and TMR were introduced into the reactor and the mixture
was stirred well to obtain a uniform liquid. Then the mixture was
heated to the designated temperature and kept constant. During
the reaction, the mass fraction of the NCO group, residual content
of HDI and IPDI monomer and the trimer content were measured
by titration using the di-n-butyl amine method according to ASTM
D2572-97, GC, GPC, respectively. As soon as the mass fraction of
the NCO group dropped to the designed value, a calculated quan-
tity of benzoyl chloride [11,12] was added to inhibit the reaction.
The mixture was continually stirred for 30 min and then the unre-
acted monomer was removed by distillation under vacuum to yield
a colorless or pale yellow liquid for the product.
2.3. Preparing the two-component polyurethane coatings
Two-component polyurethane coatings were prepared by
mixing polyols (Desmophen A365 BA/X, Desmophen A870 BA,
Hypomer FX-2460AF) with a stoichiometric amount of the HDI/IPDI
hybrid isocyanurate or cold blend of HDI trimer (Desmodur N3300)
and IPDI trimer (Desmodur Z4470 BA), and 100 ppm DBTDL
(dibutyltin dilaurate). The formulas of these coatings are listed in
Table 1 and the hybrid isocyanurate hardener sample of H-I-0.5 was
used in this work.
2.4. Characterization and analysis of HDI/IPDI hybrid
isocyanurate
2.4.1. NCO conversion
By measuring the mass fraction of NCO group, the reaction
degree was detected. The measurement of the mass fraction of NCO
Table 1
The formula of preparing polyurethane coating.
Sample Polyol
HYD-1 Desmophen A365 BA/X
BLD-1 Desmophen A365 BA/X
HYD-2 Desmophen A870 BA
BLD-2 Desmophen A870 BA
HYD-3 Hypomer FX-2460AF
BLD-3 Hypomer FX-2460AF
a
It is a HDI/IPDI hybrid isocyanurate synthesized in our lab.
b
It is a physical mixture of Desmodur N3300 and Desmodur 4470 BA.
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group was in compliance with ASTM D2572-97 and the value of
NCO conversion in the reaction was calculated in accordance with
Eq. (1).
[NCO]0 − [NCO]t
NCO conversion = × 100% (1)
[NCO]0
where [NCO]0 is the initial mass fraction of NCO group and [NCO]t
is the mass fraction of NCO group at the interval of reaction time.
2.4.2. GPC (gel permeation chromatography)
GPC was performed on Waters 1515 equipped with a series of
PS gel columns with a PS calibration. The tetrahydrofuran (THF)
acted as the eluent at flow rate of 1 mL/min at 40 ◦ C. The GPC sam-
ples were prepared from the reaction mixture every half an hour or
an hour, which were first dissolved in THF and then deactivated
by diethylamine, finally, the THF and excess diethylamine were
distilled under vacuum at 130 ◦ C. The deactivated samples were
dissolved in THF for GPC analysis.
2.4.3. GC (gas chromatography)
GC was performed on GC-3010A, Shanghai Institute of Comput-
ing Technology, The carrier gas was nitrogen. Injector and detector
temperatures were set at 300 ◦ C. The oven temperature program
was as follows: 80 ◦ C for 1 min, 80–280 ◦ C at 10 ◦ C/min, 280 ◦ C for
10 min. The test sample was prepared by dissolving reactant and
n-tetradecane (internal standard) in ethyl acetate, with the con-
centration about 3%.
2.4.4. NMR
1 H NMR (400 MHz) and 13 C NMR (100 MHz) spectra were
recorded in chloroform–d(CDCl3 ) on a Bruker AVANCE 400 FT-NMR
spectrometer.
2.4.5. ESI-MS (electrospray ionization mass spectrometry)
ESI-MS spectra were recorded on a Micromass LCT mass instru-
ment operating in the positive-ion mode. ESI-MS had been used
to analyze low molecular weight polymer or macromolecules up to
about 10,000 Da [13,14]. It was a soft ionization technique in which
exclusively molecular ions were formed with no fragmentation.
The test samples were prepared by terminating HDI/IPDI hybrid
isocyanurate by methanol to eliminate the possible side reactions
inherent to the NCO group.
2.4.6. Test methods for general properties of polyurethane
coatings
Drying time recorder (BYK Instrument) was employed to report
drying time according to ASTM D5895. The pendulum hardness
test (BYK Instrument) was performed according to ASTM D3363
with glass substrate. ASTM D4752 standard test method was per-
formed to measure the MEK resistance. The gloss and DOI of
the coatings was measured by BYK-Gardner Instrument according
to ASTM D523 and ASTM D5767-95, respectively. Impact (BYK-
Gardner Instrument) tests were performed according to ASTM
D5420 with steel Q-panel substrate.
Isocyanurate hardener HDI/IPDI in the hardener (molar ratio)
H-I-0.5a 1.45:1
Desmodur N3300/Desmodur Z4470 BAb 1.45:1
H-I-0.5 1.45:1
Desmodur N3300/Desmodur Z4470 BA 1.45:1
H-I-0.5 1.45:1
Desmodur N3300/Desmodur Z4470 BA 1.45:1
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Table 2
Synthesis conditions and results of HDI/IPDI hybrid isocyanurate.

Sample Feed formula Catalyst (wt.%) Temperature (◦ C) Time (h) NCO conversion (%)
HDI/IPDI (w/w)

H-I-0.2 1/5 0.18 65 6 18.80

H-I-0.5 1/2 0.12 65 3 21.01
H-I-1.0 1/1 0.1 60 6 22.61
H-I-1.5 3/2 0.11 65 7 22.32
H-I-2.0 2/1 0.1 65 5 21.43

3. Results and discussion O

R C R
OCN N N NCO
It is well known that HDI has much higher reactivity than mono-isocyanurate (trimer)
C C
IPDI [1]. The feed ratio of HDI and IPDI could dramatically affect O N O

the structure and composition of the HDI/IPDI hybrid isocyanu- R

NCO
rate. For mild reaction conditions, i.e., low catalyst concentration
and temperature, the reaction gave selectively the cyclic trimer O O
and not higher oligomers [15]. In our previous research of diiso- R C R C R
OCN N N N N NCO
cyanate homotrimer, the higher trimer content is obtained at low
di-isocyanurate C C C C
NCO conversion. At NCO conversion near 20–25%, there is a favor- O N O O N O
able balance between monomer utilization and trimer content. The R R
NCO NCO
reaction conditions and results of synthesizing HDI/IPDI hybrid iso-
cyanurates are tabulated in Table 2.
O O O
R C R C R C R
OCN N N N N N N NCO
tri-isocyanurate
3.1. GPC results and analysis C C C C C C
O N O O N O O N O

R R R
Both HDI and IPDI have two isocyanate groups. Inevitably, in the NCO NCO NCO
process of synthesizing HDI/IPDI hybrid isocyanurate, a mixture
mainly consisting of mono-, di- and tri-isocyanurates is formed.
Their chemical structures are shown in Fig. 1. H3C
Quantitative analysis of the isocyanurate mixture was per- CH3

formed using GPC analysis described in the literature [16,17]. With R= or —CH2—CH2—CH2—CH2—CH2—CH2—
Fig. 2(a) shows the normalized GPC curves at different reaction
C
times for sample H-I-2.0. The peaks at 9.8 min and 9.2 min corre- H3C
H2
spond to monomer, and trimer respectively, and all the peaks from
7.5 to 9.5 min are attributed to higher oligomers. As the reaction Fig. 1. The main structures of HDI/IPDI hybrid isocyanurate.
time is prolonged, it can be observed that the monomer content
decreases while trimer content increases slightly. Strimer
Quantitation of trimer content in the mixture was of primary Content of trimer in oligomer = (2)
Strimer + Smultimer
interest. Deconvolution of the peaks in the GPC spectrum was
Strimer
processed by Peakfit v4.12 software as shown in Fig. 2(b). We Content of trimer in sample = (3)
assumed that the mass fraction of each component was in accor- Smonomer + Strimer + Smultimer
dance with the area fraction of each component. Thus the trimer where Smonomer , Strimer and Smultimer are the area of monomer, trimer
content was obtained from Eq. (2) and Eq. (3), and multimer, respectively.

Fig. 2. The GPC curves at different reaction times of sample H-I-2.0 (a). Deconvolution of the peaks in the spectrum of 7.5–10.5 min for the GPC result of HDI/IPDI hybrid
isocyanurate mixture using software Peakfit v4.12 (b).

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(a) Content of trimer in oligomer (wt%) (b) Content of trimer in oligomer (wt%) (c)
100 100 Content of trimer in oligomer (wt%)
80 Content of trimer in sample (wt%)
Content of trimer in sample (wt%)
Content of trimer in sample (wt%)
70

Content of trimer (%)

Trimer content (%)
80 80

Trimer content (%)

60
51.11%
60 53.66% 50 60
52.92%
40 Distillation Distillation
40 Distillation 40
30 39.89% 45.89%
38.03%
20 20 20

10
0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 1 2 3 4 5 6 7 0 1 2 3 4 5 6
Reaction time (h) Reaction time (h) Reaction time (h)

Fig. 3. Trimer content at different reaction times: (a) H-I-0.5, (b) H-I-1.0 and (c) H-I-2.0.

content of HDI (IPDI) can be calculated by the peak areas of HDI

(IPDI) and n-tetradecane through Eq. (4),
Wi · As
C = fx · , (4)
Ws · Ai

where C is the mass fraction of monomer, fx is correction factor,

Wi is mass of internal standard sample and Ws is mass of sample.
Ai and As are the peak areas of standard sample and HDI (IPDI),
respectively.
By Eq. (4), we can calculate the free unreacted HDI and IPDI
content in the isocyanurate mixture at the interval reaction time.
The amount of each individual isocyanate incorporated into the
oligomer (reaction ratio) can be calculated by Eq. (5). The residual
monomer content and the reaction ratio of the two monomers are
shown in Table 3.

HDI (CH0 − CHt )/168

= (5)
IPDI (CI0 − CIt )/222.3

Fig. 4. GC analysis of HDI/IPDI hybrid isocyanurate. where CH0 and CI0 are initial mass fraction of HDI and IPDI, respec-
tively, and CHt and CIt are terminal mass fraction of HDI and IPDI,
respectively.
The experimental results for trimer content are shown in Fig. 3. Table 3 indicates that, the residual monomer content had
The results indicate that with increasing reaction time, more trimer decreased to an extremely low level after distillation and the
is converted into oligomer, while the total amount of trimer slightly reaction ratios of HDI/IPDI increased with the feed ratio of the
increases over time. The optimum trimer content in oligomer is monomers. This point will be discussed further in Section 3.3.
achieved, when the NCO conversion reached 20–25%. In our exper-
iments, more than 50% trimer in the oligomer before distillation 3.3. 1H NMR results and analysis
and about 40% of trimer in the final samples after distillation were
obtained. 3.3.1. Structure analysis
In order to understand the hybrid isocyanurate better, 1 H NMR
3.2. GC results and analysis of HDI isocyanurate and IPDI isocyanurate were analyzed firstly
(Fig. 5) and the chemical shifts are listed in Table 4. The study
Free unreacted diisocyanate present in the reaction mixture was of IPDI isocyanurate is more complicated than HDI isocyanurate,
removed by distillation at 170–190 ◦ C under high vacuum. The partly because of the various components of the polyisocyanate.
residual monomer content was measured by GC analysis. Inter- Moreover, it should be noticed here that the IPDI trimer exhibits
nal standardization method was adopted to calculate the monomer two distinctly different isocyanate groups [18,19].
content, with n-tetradecane as the internal standard. The 1 H NMR analysis of hybrid isocyanurate is more compli-
Fig. 4 revealed that n-tetradecane (internal standard) was elu- cated. Take the sample H-I-1.0 for example (Fig. 6), the peaks at
ting at 8.79 min, HDI was eluting at 8.51 min, and the two isomers ı3.7–5.2 ppm were attributed to the protons connected with the
of IPDI were eluting at 11.15 min and 11.53 min, respectively. The isocyanurate cycle (ı3.87 ppm for HDI and ı3.74, 4.2, 5.03 ppm for

Table 3
GC results of HDI/IPDI hybrid isocyanurate.

Sample Monomer content after reaction Feed ratio Reaction ratio Monomer content after distillationa
HDI:IPDI (mol/mol) HDI:IPDI (mol/mol)

HDI (wt.%) IPDI (wt.%) HDI (wt.%) IPDI (wt.%)

H-I-0.2 5.50 55.29 0.26 0.53 0.04 1.63

H-I-0.5 13.99 48.57 0.66 1.41 0.07 0.51
H-I-1.0 24.28 36.41 1.32 2.51 0.69 2.29
H-I-1.5 26.63 27.11 1.98 3.43 0.37 1.81
H-I-2.0 32.56 22.77 2.64 4.27 1.51 1.83
a
Condition of distillation: 30 min at 170 ◦ C and 60 min at 190 ◦ C under the vacuum of 100 Pa.

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1
Fig. 5. H NMR spectrum of HDI isocyanurate and IPDI isocyanurate.

Table 4
1
H NMR chemical shifts of HDI isocyanurate and IPDI isocyanurate.

HDI isocyanurate IPDI isocyanurate

Proton Chemical shift (ppm) Proton Chemical shift (ppm)

H1 3.29–3.32 I1 4.095–5.057
H2 1.61–1.64 I1 3.509–3.689
H3 1.37–1.44 I2 and I4 and I6 2.20; 1.2–1.4; 1.52
H4 1.37–1.44 I2 and I4 and I6 1.15–1.174; 1.403–1.48; 1.76–1.9
H5 1.61–1.64 I7 and I8 and I9 0.85–0.977; 0.993; 1.026–1.06; 1.06–1.15
H6 3.85–3.87 I7 and I8 and I9 0.85–0.977; 0.993; 1.026–1.06; 1.06–1.15
I10 3.052–3.067; 3.214–3.374
I10 3.753

1
Fig. 6. H NMR spectrum of hybrid isocyanurate (sample H-I-1.0).

IPDI). This indicates that both of HDI and IPDI participated in the
trimerization reaction.
3.3.2. Quantitative analysis
1 H NMR spectrums of HDI isocyanurate and IPDI isocyanurate
are compared in Fig. 7. In 1 H NMR spectrum IPDI isocyanurate,
there are signals below 1.06 ppm assigned to some methyl groups,
while there was no signal in this region in the 1 H NMR spectrum
of HDI isocyanurate. So we chose the region from 0.8 to 1.06 ppm
attributed to IPDI completely as internal standard and defined the
integration area as 1.00. According to the partly enlarged view of
IPDI isocyanurate spectrum (Fig. 7), the integration area from 0.8

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Fig. 7. Comparison of 1 H NMR spectrums of HDI isocyanurate and IPDI isocyanurate.

to 2.3 ppm was twice as much as that from 0.8 to 1.06 ppm. Specif-
ically, the area ratio must be constant, which was independent of
reaction condition and the feed ratio.
As shown in Table 4, the chemical shifts of proton in hybrid
isocyanurate at 0.8–2.3 ppm corresponds to 15 hydrogens (I2–I9
and I2 –I9 ) of IPDI and 8 hydrogens (H2–H5) of HDI. We defined
the integration area from 0.8 to 1.06 ppm as S1 and that from 0.8 to
2.3 ppm as S2 , thus the reaction molar ratio of HDI and IPDI can be
determined from Eq. (8).
SIPDI = 2 × S1
SHDI = S2 − 2 × S1
HDI SHDI /8
Reaction molar ratio, = (8)
IPDI SIPDI /15
where SIPDI and SHDI are the integrating area of the 15 protons
belong to IPDI and the 8 protons belong to HDI, respectively.
The results of reaction ratio calculated by 1 H NMR and GC are
compared in Table 5. The quantitative analysis results of reac-
tion ratio calculated by NMR compared well with that by GC,
which corroborates the accuracy of our data. By plotting feed
molar ratio on the abscissa and reaction molar ratio on the ordi-
nate, a linear relationship between the two values was obtained in
Fig. 8.
First, when the feed molar ratio (HDI/IPDI) was 1.0, the predicted
reaction molar ratio will be about 1.8 as the dotted line shown in
Fig. 8. This means that HDI monomer had a higher activity than IPDI
monomer in the trimerization reaction [1]. In addition, the favor-
able linear relationship indicates that the reaction ratio depends
mainly on the feed ratio and was little affected by the reaction time
or conversion. Furthermore, the linear fitting equation (9) can be
used to prepare hybrid isocyanurate with the expected reaction
ratio.
where y is the reaction molar ratio of HDI/IPDI and x is the feed
molar ratio of HDI/IPDI.
3.4. ESI-MS results and analysis
The hybrid isocyanurates were a mixture and the composition
had to be elucidated in this study. ESI-MS had been shown to be
a very efficient characterization tool for polymers under about
10,000 Da [20]. Most components in the hybrid isocyanurate can
be identified by molecular weight and quantified by the abundance
(6)
on the basis of assumption that the signal strength of abundance
(7) was independent of molecular weight [21]. The samples were ter-
minated with methanol to eliminate the possible side reactions
inherent to the –NCO group.
The ESI-MS spectrum of methanol-terminated hybrid isocyanu-
rate (H-I-2.0) is shown in Fig. 9. It is obvious from the spectrum
that the hybrid isocyanurate is a mixture containing several com-
ponents. The observed ions resulted from hydrogen attachment
to the species originally present in the solution. For example, the
base peak seen at 601 Da and the corresponding isotopes result
from hydrogen (1 Da) cationization of the methanol-terminated
HDI homotrimer. HDI monomer weighs 168 Da, therefore, the
homo-HDI trimer weighs 168 × 3 = 504 Da. The three methanol cap-
ping groups contribute 32 × 3 = 96 Da, and hydrogen adds 1 Da.
Hence, the expected ion was observed at 504 + 96 + 1 = 601 Da.
The ions peaks at 602 and 603 Da were attributed to the
methanol-terminated HDI homotrimer, which has a molecular
formula of [C27 H48 N6 O9 ]H+ . The ions at 655 and 709 Da were
attributed to the trimer with 2HDI + 1IPDI and 1HDI + 2IPDI (Fig. 10,
2 and 3), respectively. Surprisingly, no IPDI homotrimer was
detected, which is attributed to the lower activity and feed ratio of

y = 1.7088x (9)

Table 5
Comparison of the reaction ratio of HDI/IPDI calculated by 1 H NMR and GC.

No. Formula HDI/IPDI Reaction ratio

(molar)
HDI:IPDI
1
wt. Molar GC H NMR

H-I-0.2 1:5 0.26 0.53 0.48

H-I-0.5 1:2 0.66 1.41 1.45
H-I-1.0 1:1 1.32 2.51 2.54
H-I-1.5 3:2 1.98 3.43 3.25
Fig. 8. The linear relationship between reaction mole ratio and feed mole ratio in
H-I-2.0 2:1 2.64 4.27 4.42
the synthesis of HDI/IPDI hybrid isocyanurate.

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Fig. 9. The ESI-MS spectra of hybrid isocyanurate (sample H-I-2.0).

O O O O
R1 C R1 R1 C R2 R1 C R2 R2 C R2
OCN N N NCO OCN N N NCO OCN N N NCO OCN N N NCO
C C C C C C C C
O N O O N O O N O O N O
R1 R1 R2 R2
NCO NCO NCO NCO

1 2 3 4

H3C
CH3

With R1= —CH2—CH2—CH2—CH2—CH2—CH2— and R2=

C
H3C H2

Fig. 10. The chemical structures of four trimers in HDI/IPDI hybrid isocyanurate.

IPDI. The ESI-MS results demonstrate that the hybrid isocyanurate hybrid level was elevated. This is ascribed to the steric hindrance
was synthesized successfully. of IPDI which inhibits its self-trimerization, and the high activity
Furthermore, the peak at 969 Da is attributed to the HDI di- of the HDI which makes it easier to participate in the trimerization
isocyanurate, formed by the further isocyanuration reaction of HDI
mono-isocyanurate with HDI monomers. Compared to the abun-
Table 6
dance of mono-isocyanurate, that of di-isocyanurate was quite low,
Relative content of various components of the trimer by ESI-MS.
which indicated that the main component of the isocyanurate was
mono-isocyanurate. Peak (Da) Structural units Mole percentage (%)
Table 6 lists the quantitative analysis results of the four H-I-2.0 H-I-1.0 H-I-0.5
trimers by the related abundance on the basis of assumption that
601/623 3HDI + 3CH3 OH + H+ /Na+ 52.00 24.24 8.02
the signal strength of abundance was independent of molecular 655/677 2HDI + IPDI + 3CH3 OH + H+ /Na+ 39.07 46.32 36.50
weight. 709/731 HDI + 2IPDI + 3CH3 OH + H+ /Na+ 8.93 27.06 45.53
In Fig. 11, with the IPDI feed weight content in formula increas- 763/785 3IPDI + 3CH3 OH + H+ /Na+ 0 2.38 9.95
ing, the HDI homotrimer content decreased sharply while the Hybrid levela 48.00 73.38 82.03

content of IPDI homotrimer increased slightly, which indicates that a

Hybrid level: the percentage of hybrid trimer in all trimers.

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Prog. Org. Coat. (2014), http://dx.doi.org/10.1016/j.porgcoat.2014.08.017
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Table 7
Physical properties of two-component polyurethane coatings.

Test type Sample names

HYD-1 BLD-1 HYD-2 BLD-2 HYD-3 BLD-3

Drying time (BYK1, BYK2, BYK3, BYK4/h)a 0.1, 0.2, 2.8, 5.25 0.25, 0.7 2.2, 6 0.2, 0.8 3, 5.6 0.3, 0.5 3.3, >11 0.1, 0.2 0.7, 1.7 0.1, 0.2 2.8, 5.25
Pendulum hardness (König, s) (7 days) 134 123 165 150 135 127
Impact resistance (kg cm) 2 × 60 2 × 75 2 × 15 2 × 15 2 × 10 2 × 10
MEK rub (7 days) – – >200 >200 >200 >200
DOI (7 days) 93.7 78.5 92.5 87.7 89.4 75.6

91.3 89.8 91.2 89.7 83.4 84.0

Gloss (20◦ /60◦ /80◦ ) 94.3 94.6 94.9 94.4 88.8 88.9
98.3 97.2 97.8 97.2 97.2 97.3
a
According to ASTM D5895, BYK1: Touch time; BYK2: Tack free time; BYK3: Dry hard time; BYK4: Dry trough time.

3HDI trimer individual isocyanate incorporated into the oligomer (reaction

60
2HDI+IPDI trimer ratio). The polyurethane coatings prepared with HDI/IPDI hybrid
HDI+2IPDI trimer isocyanurates possessed faster drying speed, higher hardness and
3IPDI trimer gloss and better DOI than with coatings prepared from cold-blends
molar percentage of trimer(mol%)

of HDI isocyanurate and IPDI isocyanurate.

40

Acknowledgements

This research was supported by Dow Chemical Company

20 Limited. The authors wish to thank Prof. Zhiping Zhang for his
assistance.

0
30 40 50
IPDI feed weight ratio(wt %)
Fig. 11. Relationship between molar percentage of four kinds of trimer and IPDI
feed weight content.
reaction than IPDI. It should also be pointed out that the hybrid
level exceeded 80% when the IPDI content was 67 wt.% in the
feed.
3.5. Physical properties of two-component polyurethane coatings
Drying time, pendulum hardness, impact resistance, gloss and
DOI tests results are listed in Table 7. The drying time of the HDI/IPDI
hybrid hardener system is lower than that of the cold blend system,
which demonstrates that the hybrid hardener could accelerate the
drying speed of the coatings. Pendulum hardness results showed
that the coating prepared with the hybrid hardener system pos-
sessed a higher hardness than that of cold blend system. The impact
resistance was similar between the hybrid hardener system and
cold blend hardener system. The optical properties of the coatings
prepared from hybrid hardener system were also superior to the
cold blend hardener system, especially for the DOI index of the
coatings. All of these three groups of coating possessed a favorable
MEK resistance.
4. Conclusions
HDI/IPDI hybrid isocyanurates with low residual monomer
content were successfully synthesized. The trimer content in
isocyanurate was about 40 wt.% after distillation. Both GC and 1 H
NMR analysis identified a favorable linear relationship between
the feed ratio of the starting monomers and the amount of each
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Please cite this article in press as: G. Wang, et al., Synthesis of HDI/IPDI hybrid isocyanurate and its application in polyurethane coating,
Prog. Org. Coat. (2014), http://dx.doi.org/10.1016/j.porgcoat.2014.08.017