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Isocyanurate formation during rigid polyurethane foam assembly: A

mechanistic study based on: In situ IR and NMR spectroscopy

Article  in  Polymer Chemistry · September 2018

DOI: 10.1039/C8PY00637G

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Polymer
Chemistry
PAPER

Isocyanurate formation during rigid polyurethane

Cite this: Polym. Chem., 2018, 9,
foam assembly: a mechanistic study based on
4891 in situ IR and NMR spectroscopy†
A. Al Nabulsi,a D. Cozzula, *a T. Hagen,b W. Leitner c
and T. E. Müller *‡c

Received 26th April 2018,
Accepted 31st August 2018
DOI: 10.1039/c8py00637g
rsc.li/polymers
An in-depth exploratory study on the mechanism of isocyanurate formation during the assembly of rigid
PU/PIR polyurethane foams was performed thereby unravelling the role and working principle of the cata-
lyst. Mimicking the complex pattern of the foam with mono-functional equivalents, the pathways to iso-
cyanurate formation were investigated. Reactions focusing on potassium acetate as benchmark catalyst
were thereto followed by in situ IR and NMR spectroscopy. Two pathways to isocyanurate formation from
isocyanates were revealed: a one-component route via cyclotrimerization and a two-component route
via carbamate and allophanate. We show that in the presence of alcohol and along with the formation of
carbamate, isocyanurate is formed preferentially according to the two-component route in three con-
secutive steps. Allophanate, which in this study was isolated and characterized, is formed in situ in small
transient concentrations from carbamate and the excess of isocyanate. For the first time it is proven that
the allophanate intermediate undergoes an addition–elimination step with nucleophilic species to provide
the isocyanurate.

Introduction the material flexible and ductile. A high content of isocyanu-

Polyurethane–polyisocyanurate (PU/PIR) foams play a substan-
tial role in the construction market. Their efficiency as thermal
insulating materials, a trait that contributes markedly to con-
serving energy, leads to rapidly increasing relevance for redu-
cing the consumption of fossil carbon resources. The highly
crosslinked isocyanurate structure of the rigid PU/PIR foam
leads to excellent stability and high mechanical strength. The
attractivity in construction stems from the distinctive combi-
nation with a lower density and weight compared to many
other conventional materials.1–6 This is in addition to the low
thermal conductivity and excellent flame retardant properties
of rigid PU/PIR foams.1,2,6–10 Strikingly these properties can be
adjusted in a wide range by controlling the ratio of urethane to
isocyanurate moieties. A high content of urethane moieties
provides a large proportion of linear connections that render
a atoms” to the corresponding carbamoyl derivatives.13–19 In
CAT Catalytic Center, RWTH Aachen University, Worringerweg 2, 52074 Aachen, DE,
Germany. E-mail: Daniela.Cozzula@catalyticcenter.rwth-aachen.de
b
COVESTRO Deutschland AG, Kaiser-Wilhelm-Allee 60, 51373 Leverkusen, DE,
Germany
c
ITMC, RWTH Aachen University, Worringerweg 1, 52074 Aachen, DE, Germany.
E-mail: Thomas.Ernst.Mueller@itmc.rwth-aachen.de
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
c8py00637g
‡ Current address: RFH Köln, Schaevenstraße 1 a-b, 50676 Köln, Germany (DE).
rate moieties provides a highly cross-linked dense network
that renders the material harder, yet on occasion brittle. In
controlling these structure–property relationships, the choice
of the catalyst and the mechanism of isocyanurate formation
play a key role.
The general mechanism for the anionic trimerization of iso-
cyanates is widely accepted. It was proposed first by Reymore
et al.11,12 and was illustrated later by Hoffman, who prepared
triphenyl isocyanurate from phenyl isocyanate using potass-
ium acetate as catalyst.4 According to this mechanism, the
nucleophile acetate adds to an isocyanate molecule to give a
stable intermediate anion that, in the presence of excess iso-
cyanate, undergoes intramolecular cyclization thereby regener-
ating the acetate catalyst.11
Alternative to the cyclotrimerization of isocyanate, the iso-
cyanurate is also formed through the stepwise reaction
between alcohol and excess isocyanate. Isocyanates readily
react with compounds comprising so-called “active hydrogen
case of alcohol (R′OH) and isocyanate (RNCO), carbamate
(RNHCOOR′) is formed in the first step. The latter is trans-
formed with excess isocyanate into the corresponding allopha-
nate (RNHCONRCOOR′) that is converted into the stable iso-
cyanurate thereby regenerating the starting alcohol.13,14,16,18
Despite a number of studies on the chemistry of isocyanurates,
the details of the illustrated general mechanism have not been

This journal is © The Royal Society of Chemistry 2018 Polym. Chem., 2018, 9, 4891–4899 | 4891
Paper Polymer Chemistry

outlined. In addition, the role of intermediates in the complex

reaction network of PU/PIR foams has remained unclear. By
investigating the mechanism of isocyanate trimerization with
modern spectroscopic techniques, we targeted on the one
hand at generating a fundamental understanding of catalysis
in polyurethane material manufacture, and on the other hand
to set the base for the development of more efficient catalysts.
At present new catalysts are put forward for controlling the
ratio of urethane to isocyanurate moieties.4,20–22 Nevertheless
potassium acetate remains to be the standard catalyst in the
Scheme 1 Mimic reaction chosen to investigate the mechanism of iso-
industrial scale production of PU/PIR foams.
cyanurate formation during rigid polyurethane foam assembly.
The target of this study was to explore in-depth the reaction
network that occurs during the formation of rigid PU/PIR
foams. In that way, we aimed to unravel the role of reaction
tion was performed in a steel reactor equipped with a highly
intermediates and understand the working principles of the
efficient cooling system. Propylene carbonate was selected as
benchmark catalyst potassium acetate. Making use of mono-
solvent due to the fact that the polarity resembles the settings
functional reagents to mimic the complex features of the
in the foam, for its high boiling point and as in IR spec-
foam, the reactions were followed in situ by IR or NMR spec-
troscopy the bands do not interfere with the region of interest.
troscopy. To gain more detailed insight into the reaction
After injecting a solution of acetate (0.1 mol% with respect to
network the nucleophilicity of the catalyst, the ratio of isocya-
pTI) and DEME into a solution of pTI, the intensity of the
nate/alcohol and the catalyst concentration were varied.
characteristic signal of the asymmetric NvCvO stretch of pTI
at 2274 cm−1 began to decrease rapidly (Fig. 1), while two
other signals rapidly increased in the characteristic region for
Results and discussion the CvO stretch. Based on reported data,31 the signal at
Mimic reaction 1728 cm−1 is attributed to the CvO stretch of the carbamate
product (CRB) and the signal at 1704 cm−1 is attributed to the
In the system of PU/PIR foams, the polymer network is gener-
CvO stretch of isocyanurate (ISR).32
ated by reacting polyisocyanates such as methylene diphenyl
In the presence of KOAc, 90% of pTI was converted within
diisocyanate and its higher oligomers (MDI) with polyols.
of 1.2 min (Fig. 1, top) at an initial rate of 2.50 × 10−3 L mol−1 s−1.
Additives tailor the properties of the PU/PIR foams to the
In the presence of KOAcF, more time (6 min) was required to
specific application. For investigating the mechanism of iso-
obtain the same conversion of pTI (Fig. 1, bottom). The initial
cyanurate formation, we decided to mimic the complex reac-
rate of isocyanate consumption was 1.28 × 10−3 L mol−1 s−1. The
tion system of the PU/PIR foam with related mono-functional
lower activity of KOAcF can be related to the lower nucleophilicity
substrates thereby facilitating the analysis of the spectra as well
of the carboxylate group. In both cases the two products of the
as the reaction products. p-Tolyl isocyanate (pTI) and diethylene
reaction, CRB and ISR, were obtained in the same molar ratio of
glycol methyl ether (DEME) were selected as mimic substrates
1.2 : 1. As the reaction was performed with 2.5 fold excess of pTI
for MDI and ethylene glycol units, respectively, that are com-
(pTI : DEME 3.5 : 1), this means that the isocyanate (28.6%)
monly present in commercial polyether polyols used in PU/PIR
reacted preferentially with the alcohol to carbamate and that only
formulations. Using potassium acetate as nucleophilic catalyst,
the remaining isocyanate (71.4%) trimerized to isocyanurate
two main products are expected: 2-(2-methoxyethoxy) ethyl
(Scheme 1). As the formation of carbamate prevails over isocyanu-
p-tolyl carbamate (CRB) as product of the addition reaction
rate, yet high isocyanurate content is essential for excellent pro-
between one alcohol molecule and one isocyanate molecule,
perties of rigid PU/PIR foams, the understanding of the pathways
and tri-p-tolyl-s-triazinane-2,4,6-trione (ISR) as product of the tri-
to isocyanurate formation is of great importance. It also opens the
merization reaction of three isocyanate molecules (Scheme 1).
prospect to developing catalysts that would be more selective
Kinetic study towards isocyanurate formation.

To obtain insight into the reaction kinetics and the influence

of the nucleophilicity of the catalyst, the catalytic activity of
potassium acetate (KOAc) and potassium trifluoroacetate
(KOAcF) was compared. Mimicking the conditions of real foam
formulations, the reaction was performed at a fixed molar
ratio of pTI : DEME (3.5 : 1) at 70 °C. Owing to its well resolved
spectral features, in situ IR spectroscopy was selected to
monitor the components that take part in the reaction.23–25 To
ensure isothermal conditions despite the high exothermicity
of the reaction between isocyanate and alcohol,26–30 the reac-
Reaction pathways
In the literature,11 two competitive reaction pathways are
described to explain the formation of isocyanurate: via the
cyclotrimerization of isocyanate (Pathway A); and via three con-
secutive steps involving alcohol (Pathway B) where: (i) alcohol
reacts with isocyanate to form carbamate, (ii) carbamate reacts
with another molecule of isocyanate to form allophanate and
(iii) allophanate reacts with a third molecule of isocyanate to
form isocyanurate thereby liberating alcohol (Scheme 2).

4892 | Polym. Chem., 2018, 9, 4891–4899 This journal is © The Royal Society of Chemistry 2018
Polymer Chemistry Paper

Trimerization in the absence of alcohol

The reaction pathway of isocyanurate formation in the absence
of alcohol was investigated first. The trimerization of pTI with
KOAcF (stoichiometric ratio of 1 : 1) was followed with in situ
NMR spectroscopy. KOAcF was selected as catalyst as its lower
activity compared to KOAc allows a more precise recording of
spectra and, thus, more facile monitoring of the reaction com-
ponents. The experiment was carried out in deuterated
dimethyl sulfoxide (DMSO-d6) at 25 °C and the spectra were
recorded every two minutes. pTI was identified by the signal of
the methyl group at the aromatic ring at 2.28 ppm. The
formation of isocyanurate (ISR) was followed by the methyl
group of the aromatic rings at 2.34 ppm. The changes in the
intensity and the chemical shift of these characteristic signals
were followed over 19.5 h. All chemical shifts were referenced
to the shift of DMSO-d6 at 2.50 ppm. The most significant
spectra are shown in Fig. 2 concentrating for clarity at the
beginning and the end of the reaction.
The high-intensity signal at 2.28 ppm (85.5 mol%) in the
spectrum recorded at the early stage of the reaction (2 min) is
attributed readily to pTI. A low intensity signal assigned to ISR
emerged at 2.34 ppm (1.8 mol%). Noteworthy, three new
signals with low intensity were visible in the methyl region at
2.22 (signal A), 2.24 (signal B) and 2.36 ppm (signal C). The
spectrum recorded at 4 min showed a decrease in the signal
intensity of pTI (83.4 mol%) and a corresponding increase in
the signal intensity of ISR (2.9 mol%). Also, the intensities of
the three signals A to C increased with time. The spectrum
recorded at 8 min revealed significant changes in the methyl
region: a considerable decrease in the signal intensity of pTI
(75.6 mol%), a correspondingly strong increase in the signal

Fig. 1 Time-resolved in situ IR spectra showing the consumption of

p-tolylisocyanate ( pTI) when reacted with diethylene glycol methyl
ether (DEME) using KOAc as catalyst (top) in comparison to KOAcF
(bottom).

Fig. 2 Selected 1H-NMR spectra of the reaction mixture of pTI and

Scheme 2 Competitive reaction pathways to the formation of isocya- KOAcF recorded over 19.5 h. For clarity, only the region covering chemi-
nurates from the reaction of alcohols with excess isocyanate (Ar = cal shifts between 2.16 and 2.38 ppm is shown. pTI ( p-tolylisocyanate);
RC6H4). ISR (isocyanurate); urea (Ar–NHC(O)NH–Ar).

This journal is © The Royal Society of Chemistry 2018 Polym. Chem., 2018, 9, 4891–4899 | 4893
Paper
intensity of ISR (8.1 mol%) and an increase in the signal inten-
sity of A with a small shift to 2.20 ppm (5.8 mol%). The signals
B and C also shifted slightly to 2.23 and 2.35 ppm. At 14 min
(not shown for clarity), there was a continued decrease in the
signal intensity of pTI (62.2 mol%) and an increase in the
signal intensity of ISR (17.6 mol%). The other three signals
slightly shifted: signal A at 2.20 ppm shifted to 2.19 ppm,
signal B overlapped with the signal of a substituted urea
(Ar–NHC(O)NH–Ar) at 2.23 ppm and signal C shifted to
2.35 ppm and partially overlapped with the signal of ISR. The
formation of the substituted urea is attributed to the reaction
of pTI with traces of water in the DMSO-d6. At 24 min, the
intensity of the pTI signal was decreased further (42.7 mol%),
while the intensities of the characteristic signals of ISR
(30.8 mol%) and signal A (13.2 mol%) were increased. The
signals B and C were no longer distinguishable in the spectra
due to spectral overlap with other bands. After the projected
transition through the spectrum at 120 min, the spectrum
recorded at 1170 min (19.5 h) showed only two signals in the
methyl region in addition to the urea signal: ISR at 2.34 ppm
(47.2 mol%) and signal A (30.4 mol%) at 2.18 ppm.
According to the general mechanism for the anionic trimer-
ization of isocyanates that was proposed by Reymore and illus-
trated by Hoffman4,11 the formation of isocyanurate goes
through three anionic intermediates (Scheme 3): the nucleo-
philic anion adds to one isocyanate molecule to produce a first
intermediate anion (I1). Then, the addition of this intermedi-
ate to another isocyanate molecule produces a second inter-
mediate (I2) that adds to a yet another isocyanate molecule to
produce the third intermediate (I3). During a subsequent ring-
closure step the latter forms the isocyanurate thereby releasing
the anion. If one of the steps is rate determining, one specific
intermediate is expected to be observed. If similar reaction
rates were present for the three steps, three intermediates are
expected to be observed.
Scheme 3 Established catalytic cycle of the isocyanurate formation via
the anionic trimerization of isocyanate ( pathway A).
4894 | Polym. Chem., 2018, 9, 4891–4899
Polymer Chemistry
To learn, if signals A to C belong to one of the three
expected intermediates, the in situ NMR spectra of the reaction
between pTI and KOAcF were analysed in further detail. Note
that the intensity of signal A steadily increased in intensity
during the reaction. Consistent with the initial ratio of isocya-
nate to acetate, even the highest intensity of signal A in the
spectrum recorded at 19.5 h was low compared the starting
materials and products. Likewise, the intensity of signals B
and C was low passing through a shallow maximum shortly
after the start of the reaction. Close inspection of the aromatic
region of the 1H-NMR spectrum recorded at 19.5 h revealed
two doublets at 7.23 and 6.88 ppm that are part of an AA′ BB′
system (Fig. 3). Closer inspection of the recorded spectra
revealed that the chemical shift of both doublets shifted
during the reaction, while the same difference in frequency
(213 Hz) was maintained. The singlet at 2.18 ppm (signal A) is
characteristic of the methyl protons of a tolyl substituent. The
three signals have relative integrals of 2 : 2 : 3. Positions and
integrals match the ones observed for the isolated intermedi-
ate I1 (see ESI†). Likewise, we tentatively assign the singlets at
2.24 (signal B) and 2.36 ppm (signal C) to the methyl protons
of the distal tolyl substituent of I2 and I3, respectively.
To verify the structure of intermediate I1, a sample of the
reaction mixture was analysed by ESI-MS spectroscopy.33–36
The signals with high abundance in the positive-ion mode are
listed in Table 1. Most importantly, the ion mass signal at
m/z = 279.97 with relative abundance of 62% is assigned to
2,2,2-trifluoroacetic p-tolylcarbamic anhydride associated with
an additional methanol molecule. This species is attributed to
the addition of CF3COO− to pTI, and the methanol is due to
the use of methanol as medium for the ESI-MS analysis. The
corresponding ion mass of intermediate I1 after losing one
molecule of carbon dioxide was also observed (m/z = 242.0).
The ion mass at m/z = 438.12 is assigned to ISR. The corres-
Fig. 3 Selected 1H-NMR spectra of the reaction mixture of pTI and
KOAcF recorded over 19.5 h. For clarity, only the aromatic region
between 6.78 and 7.45 ppm is shown. pTI ( p-tolylisocyanate); ISR (iso-
cyanurate); urea (Ar–NHC(O)NH–Ar).
This journal is © The Royal Society of Chemistry 2018
Polymer Chemistry Paper

Table 1 High abundance signals observed from the positive-ion mode which continued to accumulate until the complete conversion
of ESI-MS analysis of the reaction mixture of pTI and KOAcF at 19.5 h of pTI.

m/z Relative abundance [%] Assignment Trimerization in the presence of alcohol

190.91 61 (CF3COOK) K+ The reaction pathway of isocyanurate formation in the pres-
279.97 62
ence of alcohol was investigated thereafter. The 1H-NMR study
was repeated (vide supra), whereby the reaction was performed
438.12 50 (Isocyanurate) K+ in the presence of DEME at a molar ratio of 3.5 : 1 : 0.002
494.81 100 (CF3COOK)3 K+ ( pTI : DEME : KOAcF). Along with the characteristic signals of
798.71 12 (CF3COOK)5 K+
pTI and ISR, CRB and the corresponding allophanate (2-(2-
methoxyethoxy) ethyl p-tolyl ( p-tolylcarbamoyl) carbamate,
APH) were identified by the resonance of their –COOCH2
ponding ion masses of ISR plus an additional water molecule
group at 4.18 and 4.23 ppm, respectively. The alcohol (DEME)
(m/z = 456.83) and an additional molecule of CF3COOK (m/z =
was followed by the –OH signal that, in our case, was observed
590.07) were also observed. The ion masses at m/z = 190.91,
at 4.57 ppm.
494.81 and 798.81 are readily assigned to [(CF3COOK)n K]+
The 1H-NMR spectrum at 1 min showed high-intensity
with n = 1, 3 and 5, respectively. The formation of singly
signals at 2.27 ppm (76.8 mol%) and 4.57 ppm (21.9 mol%),
charged ions of [(CF3COOM)n M]+ and [(CF3COOM)n CF3COO]−
attributed to pTI and DEME in the initial ratio (Fig. 5). At
in both positive- and negative ionization modes was reported
37 min, a high-intensity signal at 4.18 ppm (21.3 mol%) as
by Moini et al.37 In that study, alkali–metal trifluoroacetates
well as a low-intensity signal at 4.23 ppm (3.9 mol%) attributed
had been used as calibration standards for ESI-MS. The nega-
to the –COOCH2 groups of the formed CRB and APH were
tive-ion mode provided the corresponding negative ions for
observed. In parallel, the intensity of the methyl signal of pTI
intermediate I1, ISR and [(CF3COOK)n CF3COO]− with n = 1, 3
(62.7 mol%) and the –OH signal of DEME (8.6 mol%)
and 5 (see ESI†). Thus, the ESI-MS data confirm the formation
decreased. In the spectrum at 79 min, there was a considerable
of intermediate I1 as intermediate during the anionic trimeri-
decrease in the intensity of the signals of pTI (49.2 mol%). The
zation of isocyanate and at the same time provide additional
spectrum revealed a small increase in the signal intensities of
evidence for the attribution of signal A to this intermediate.
CRB and APH (26.3 and 7.5 mol%) and the appearance of the
To obtain a reaction profile, the molar ratio was calculated
characteristic methyl signal of ISR (8.1 mol%). At 118 min, the
for each component (mol%) from the normalized integral of
spectrum showed a decrease in the signal intensities of pTI
the corresponding characteristic signal to the sum of all nor-
(40.3 mol%) and APH (6.1 mol%), while a small increase in
malized integrals (see ESI†) and plotted against time. The
the signal intensity of CRB (28.4 mol%) and a considerable
profile (Fig. 4) reveals two phases: a first phase commencing
increase in the signal intensity of ISR (14.9 mol%) were
from mixing the reagents to about 120 min and a second
observed. In the spectrum recorded at 18.3 h, the pTI signal
phase ranging from 120 min to full conversion of isocyanate.
During the first phase, isocyanate was consumed at high rate
according to a pseudo-first order reaction. Trimer and species
I1 formed as main products, reaching a maximum concen-
tration at 120 min. In the second phase, pTI was consumed at
much lower rate. Trimer remained unchanged, while the
molar ratio of signal A increased slightly towards the end of
the reaction. It was also observed that the decrease in the
molar ratio of pTI was equal to the increase in species I1,

Fig. 5 Selected 1H-NMR spectra of the reaction mixture of pTI and

DEME in the presence of the catalyst KOAcF recorded over 18.3 h. For
clarity, the aromatic region is omitted. pTI ( p-tolylisocyanate); CBR (car-
Fig. 4 Reaction profile obtained for the reaction of p-tolyl isocyanate bamate), ISR (isocyanurate), DEME (diethylene glycol methyl ether), APH
( pTI) with KOAcF to isocyanurate (ISR) and species I1. (allophanate).

This journal is © The Royal Society of Chemistry 2018 Polym. Chem., 2018, 9, 4891–4899 | 4895
Paper
was no longer visible and the intensity of the signal of DEME
was low (5.0 mol%). The intensities of the signal of CRB and
ISR were high (50.5 and 35.6 mol%, respectively). At 4.23 ppm,
no signal was detected indicating the complete consumption
of allophanate (Fig. 5).
To confirm the formation of allophanate during the experi-
ment, a sample taken from the reaction mixture was analysed
by HPLC-MS. Clearly an ion mass at m/z = 387 was observed
attributed to the presence of APH in the reaction mixture.
A sample of pure APH was thereafter obtained as solution in
methanol by preparative HPLC chromatography and analysed
in detail by 1H-NMR spectroscopy and COSY (see ESI†).
The obtained reaction profile, shown in Fig. 6, reveals three
phases preceding the full conversion of isocyanate and the for-
mation of isocyanurate: (i) a first phase from mixing of the
reagents to 37 min (carbamate phase), (ii) a second phase
from the 37 min to around 2 h (allophanate phase) and (iii) a
third phase from about 2 h to the full conversion of isocyanate
(isocyanurate phase).
During the carbamate phase (Phase i), pTI and DEME
reacted at high rates and the corresponding carbamate (CRB)
formed as main product following roughly a second-order reac-
tion. A small amount of APH was also produced. ISR formation
was not observed at this stage of the reaction. In the allopha-
nate phase (Phase ii), pTI and DEME were consumed albeit at
a lower rate, and consequently the formation of CRB was
slower. The concentration of APH increased further during
this phase reaching a maximum at 79 min. This was
accompanied by considerable formation of ISR. In the isocya-
nurate phase (Phase iii), pTI was consumed together with APH
until complete conversion was obtained, while the concen-
tration of DEME remained almost unchanged. In parallel, CRB
and ISR were formed steadily to reach a maximum concen-
tration at the end of the reaction. During the carbamate phase,
pTI obviously reacted with DEME to the corresponding CRB.
An excess of pTI and a considerable concentration of CRB are
required to achieve the formation of APH as a consecutive
product. The allophanate phase seems to be the critical step in
Fig. 6 Reaction profile recorded for the mixture of pTI and DEME in the
presence of the catalyst KOAcF. pTI ( p-tolylisocyanate), CBR (carbamate),
ISR (isocyanurate), DEME (diethylene glycol methyl ether), APH
(allophanate).
4896 | Polym. Chem., 2018, 9, 4891–4899
Polymer Chemistry
the formation of isocyanurate. Formation of ISR commences,
when APH reaches a critical concentration of 8% molar ratio.
Thus, isocyanurate is a consecutive product in the further reac-
tion with allophanate rendering allophanate a key intermedi-
ate in the formation of isocyanurate, when alcohol is present.
Consistent with the allophanate phase, ISR formation takes
place during the third phase, but only, when APH is present in
the reaction mixture.
Allophanate as key intermediate
During the reaction between pTI and DEME the formation of
APH clearly reached a maximum before the phase of isocyanu-
rate formation. In order to determine whether the allophanate
was formed from carbamate in a consecutive reaction with iso-
cyanate, another experiment was carried out: the alcohol was
introduced as carbamate and the reaction with isocyanate per-
formed at a ratio pTI : CRB of 1 : 1 in the presence of stoichio-
metric KOAcF. Due to the higher concentration of KOAcF, the
rate of the reaction was expected to be high. Therefore, we
focused on the spectra at the early stage (1, 3, 6 and 12 min)
and final stage (56 min and 20 h, Fig. 7) of the reaction.
At 1 min, the 1H-NMR spectrum showed high-intensity
signals at 2.27 and 4.18 ppm, attributed to pTI (41.7 mol%)
and CRB (51.7 mol%), respectively. A low-intensity signal at
4.23 ppm for APH (4.1 mol%) was also detected. Already at
3 min, the intensities of the characteristic methyl signal of pTI
(29.5 mol%) and –COOCH2 signal of CRB (45.3 mol%) rapidly
decreased, while there was a significant increase in the inten-
sity of the characteristic –COOCH2 signal of APH (13.8 mol%).
At this stage, both the characteristic methyl signal of ISR
(6.1 mol%) at 2.34 ppm and the –OH group of DEME
(2.4 mol%) at 4.67 ppm were observed. Note that DEME was
the corresponding alcohol of the carbamate. The signal inten-
sity of pTI (21.4 mol%) continued to decrease in the spectrum
Fig. 7 Selected 1H-NMR spectra of the reaction mixture of pTI and CRB
in the presence of KOAcF recorded over 20 h. For clarity, the aromatic
region is omitted. pTI ( p-tolylisocyanate); CBR (carbamate), ISR (isocya-
nurate), DEME (diethylene glycol methyl ether), APH (allophanate).
This journal is © The Royal Society of Chemistry 2018
Polymer Chemistry
recorded at 6 min, while the signal intensity of CRB increased
(47.4 mol%). In comparison to the previous spectrum, APH
showed a slight decrease in the signal intensity (13.2 mol%).
On the other hand, an increase in the signal intensity of ISR
(10.3 mol%) accompanied with an increase in the –OH signal
of DEME (5.1 mol%) was observed. While the intensity of pTI
and APH signals had steadily decreased at 6 min, the intensity
of CRB, ISR and DEME signals had continued to increase. The
signals of pTI (2.6 mol%) had a very low intensity at 56 min; so
did the signal of APH (1.5 mol%). The signal of CRB
(57.3 mol%), ISR (19.4 mol%) and DEME (13.2 mol%) had
higher intensities. Both pTI and APH signals were no longer
observed in the spectra recorded afterwards. Signals of
CRB and ISR showed a slight increase (59.4 and 22.1 mol%,
respectively). At 20 h, no further changes were observed in the
spectra (Fig. 7).
The reaction profile (Fig. 8) clearly reveals the formation
and consumption of allophanate. After a first phase from
mixing of the reagents to 3 min (allophanate phase), a second
phase to the full conversion of isocyanate (isocyanurate phase)
is observed. During the first phase, pTI and CRB were con-
sumed at high rates. APH was formed as the main product,
reaching a maximum concentration at 3 min. A significant
amount of ISR was also formed. In the second phase, pTI and
APH were consumed at lower rates, while CRB showed an unex-
pected increase. ISR was formed during the second phase
until complete conversion of pTI had been obtained. Although
CRB replaced DEME as the starting material, the formation of
DEME was clearly observed accompanied by the formation of
ISR. Thus, allophanate is a consecutive product formed by the
reaction of carbamate and isocyanate. In the second phase, the
formation of isocyanurate is accompanied by the (unforeseen)
formation of carbamate and alcohol.
These observations are readily explained by two analogous
mechanistic routes (Scheme 4), both of which lead to the for-
mation of isocyanurate: nucleophilic addition of the inter-
mediate I1 to the carbonyl group in α or β position of the allo-
phanate molecule accompanied by elimination of carbamate
or alcohol, respectively.
Fig. 8 Reaction profile of a mixture of pTI and CRB in the presence of
KOAcF. pTI ( p-tolylisocyanate); CBR (carbamate), ISR (isocyanurate),
DEME (diethylene glycol methyl ether), APH (allophanate).
This journal is © The Royal Society of Chemistry 2018
Paper
Scheme 4 Feasible routes for the formation of ISR (isocyanurate) from
APH (allophanate).
• Reaction of I1 with the carbonyl group in α position leads
to the formation of carbamate (CRB) and intermediate I2.
Since the generation of uretdione by an intramolecular
mechanism of I2 was not observed, the reaction continues and
I2 reacts further with another molecule of pTI to form inter-
mediate I3. The latter undergoes an intramolecular cyclization.
Thereby, the lone electron pair of the terminal nitrogen moiety
is added to the carbonyl group γ and the catalytic nucleophile
departs with an electron pair to form the energetically
favoured six-membered ring (ISR).
• Reaction of I1 with the carbonyl group in β position leads
to the release of alcohol (DEME) and formation of intermedi-
ate I3 that eventually produces the isocyanurate (ISR).
Parallel pathways to isocyanurate formation
Two competitive pathways in the reaction of isocyanate to iso-
cyanurate were identified (Scheme 5):
Pathway A: Cyclotrimerization of isocyanate to isocyanurate
(anionic route), where the nucleophilic anion adds to a first
molecule of isocyanate to form the intermediate I1. The latter
reacts further with two further molecules of isocyanate to form
intermediates I2 and I3, respectively. The isocyanurate ring is
then formed via an intramolecular nucleophilic substitution,
by which the nucleophilic anion departs for a new catalytic
cycle.
Pathway B: The formation of isocyanurate via three consecu-
tive steps, in which the allophanate plays a key role as inter-
mediate (allophanate route). In this pathway, a molecule of iso-
cyanate adds to a molecule of alcohol to form the corres-
ponding carbamate. Another molecule of isocyanate adds to
the carbamate to form the corresponding allophanate. The
third step consists of nucleophilic addition of the intermediate
I1 to the formed allophanate following one of two analogous
routes that lead both to the formation of the isocyanurate ring
and elimination of either carbamate or alcohol. To promote
the formation of isocyanurate in this step, a significant con-
centration of the allophanate is required to be able to react
with the intermediate I1 that is formed in situ in a catalytic
amount. Also with regard to the preferred reaction pathway, a
Polym. Chem., 2018, 9, 4891–4899 | 4897
Paper
Scheme 5 Competitive pathways of the reaction network of isocyanu-
rate formation.
high concentration of allophanate ought to promote pathway
B. As shown above, isocyanurate formation accelerates once
the concentration of allophanate rises to an 8% molar ratio.
More detailed analysis of the kinetic profiles allows for first
insight into the rate determining steps. The spectra clearly
revealed the prevalence of I1 and allophanate as reaction inter-
mediates, while I2 and I3 were not detected. Thus, in the
anionic route, the reaction of I1 with isocyanate to species I2
and, in the allophanate route, the reaction of I1 with allopha-
nate to intermediate I2 or I3 ought to be rate determining. The
actual ring closure step that provides isocyanurate once inter-
mediate I3 had been obtained ought to be quite fast.
PU/PIR foam formulation
To confirm the catalyst activity in a PU/PIR foam formulation,
MDI was reacted with polyol in the presence of KOAc (ratio
3.5 : 1 : 0.002) and pentane as blowing agent. Analysis of
samples taken from the core and the surface of the foam (see
ESI†) revealed the formation of carbamate and isocyanurate.
The isocyanurate content was higher in the sample taken from
the core of the PU/PIR foam. Further, residual isocyanate was
observed in both samples. In the foam formulation, the high
temperatures up to 200 °C in the core of the foam will favour
the allophanate route compared to the anionic route (NMR
characterization of allophanate as intermediate in PU system
4898 | Polym. Chem., 2018, 9, 4891–4899
Polymer Chemistry
is also reported in literature).38 The rapidly increasing viscosity
gives rise to diffusion limitations that prevent complete con-
version of the isocyanate moieties. Despite closer inspection of
the spectra, the bands of intermediates were obscured by the
intense bands of the main products.
Conclusions
In summary, we have explored in-depth the reaction network
of isocyanurate formation during the reaction of isocyanates
and alcohols. The study has unravelled the fundamental role
of a nucleophilic catalyst as simple as potassium acetate and
resolved a detailed reaction mechanism. Thereby the pro-
perties of the catalyst have to be well balanced. As a strong
nucleophile the catalyst is more prone to bind the isocyanate
molecule while, at the same time, it has to be a good leaving
group to facilitate the ring closure step and, thus, formation of
isocyanurate. In the catalytic cycle, in situ formed species I1 plays
a key role; its importance as longer-living intermediate was
demonstrated. In the presence of alcohol, the reaction proceeds
through a preferred mechanism via carbamate and allophanate
followed by ring closure to isocyanurate. Allophanate was
demonstrated to be a consecutive product of the reaction
between the carbamate and the isocyanate. Reaction of the inter-
mediate I1 with one of the carbonyl groups of the allophanate
molecule leads to the elimination of the respective carbamate or
alcohol. This is followed by ring closure to isocyanurate.
Due to the significant progress in the development of more
active and selective catalysts for isocyanurate formation,22 a
quantitative leap concerning catalysts that provide increased
activity and improved selectivity to isocyanurate compared to
conventional catalysts ought to be feasible. This study concern-
ing the pathway of isocyanurate formation might provide fresh
impetus to generate the necessary new ideas of how to tune
the catalytic cycle.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
Financial support from Covestro Deutschland AG and fruitful
discussions with Dr Bolko Raffel are gratefully acknowledged.
DC thanks Dr Kai Laemmerhold (Covestro Deutschland AG)
for the support given. We sincerely thank Ms. Ines Bachmann-
Remy from the ITMC department at RWTH Aachen University
for performing the in situ NMR experiments.
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