BLOCKED AND DEBLOCKED ISOCYANATE WIHT NaHSO3

PREVIEW

Introduction
Isocyanate is one of wood adhesive with excellent bonding properties, water resistance, aging
resistance, no formaldehyde emission, and other pollution problems. It is to adapt to wide range of bonding
materials (Tan et al., 2011). Unfortunately such systems are too reactive at room temperature, because of
their sensitivity before cure to moisture either from solvents, resins or pigments, or from high humidity
under application condition (Wicks and Wicks 1975). The high reactivity and high toxicity of isocyanates do
not allow their storage or their use in one component systems. This system has a short pot life, and the
operation is difficult. It is due to high reactivity of isocyanate group at room temperature, so this monomer is
difficult to deposit for a long period. Blocked isocyanate is a solution to overcome these drawbacks (Lou
and Di, 2013).
A blocked isocyanate is an adduct containing comparatively weak bond formed by reaction between
an isocyanate and a compound containing an active hydrogen atom, and shows the advantage of quite long
shelf life because the active N=C=O groups are masked and protected (Lou and Di, 2013). The isocyanate
blocking technology is great significance to further development and application of isocyanate adhesives.
The blocked isocyanate adhesive applied as wood adhesive should be unblocked under less than 100C
(Zhang et al., 2011). Blocked isocyanates have wide spread use in many coatings areas: automotive,
maintenance, and industrial finishing (Wicks and Wicks, 2001). Furthermore, blocked isocyanates are stable
at room temperature in the presence of polyols and waterborne. They were dissociated at different
temperatures depending upon the chemical nature of the group adjacent to the urethane linkage, to generate
free isocyanate, which react with hydroxyl groups to give perfect performance of adhesive (Engonga and
Marchetti, 2000). The overall reaction in the case of blocked isocyanate formation can be seen at scheme 1,
where NaHSO3 was the blocking agent.

O
N=C=O

N=C=O

CH2

NH

N=C=O

NaHSO3

CH2

Scheme 1. Preparation of blocked and deblocked polyisocyanates

SO3Na

CH2

NH

O
C

SO3Na

NH

CH2

SO3Na

As an abundant blocking agent, NaHSO3 has special properties such as low unblocking temperature,
low price, and no pollution. Bisulfites have been widely used due to their low deblocking temperature
compared to alcohols, phenols, oximes, and caprolactom. They have been the most favoured of blocking
groups for isocyanates in waterborne solution. Bisulfite blocked isocyanates are prepared by reacting with
isocyanates in aqueous solutions of sodium bisulfite to give water-soluble blocked isocyanates (Zhang et al.,
2011). During the blocking procedure, low molecular weight sodium bisulfite must be dissolved in water,
and due to the greater reactivity of isocyanates and hydroxyl compound, especially water, the reactions are
devoid of undesirable side reactions (Iyer et al., 2002). The hydrolysis of sulfite blocked isocyanates is pH
dependent, being slowest at low pH, blocked aromatic isocyanates undergo more rapid hydrolysis than
aliphatic derivatives (Wicks and Wicks, 1999).
However, the more important deblocking reaction mechanism was still not investigated. The most
common methods of monitoring deblocking reactions and determining deblocking temperature are Fourier
transform infrared spectrometry (FTIR) (Zhang et al., 2011), differential scanning calorimetry (DSC),
thermogravimetry analysis (TGA) and solid state NMR (Wicks and Wicks, 1999). The use of FTIR in
combination with DSC is particularly effective for studying curing mechanisms. TGA has been used to
determine the kinetic parameters of deblocking reactions (Kordomenos et al., 1982). Solid state

13

C-NMR

can be used to track the intensity of carbon atoms within the blocking group, which become more intense
after deblocking reaction (Cholli et al., 1983; Zuo et al., 2012).

Materials and instrument

Polymer methylene diphenyl isocyanate (PMDI), polyethylene glycol polyglycol (PEG, MW400),
1,4-dioxanel, sodium bisulphite, and ethanol were used for this research. DSC thermal analyser using
alumina as a reference, FTIR measurement for infrared spectra of samples, TGA were used for the
investigation of the blocking and deblocking reaction of blocked isocyanate (Zhang et al., 2011).

Preparation of blocked isocyanate

First, the flask was refrigated at the temperature of 0-25C with a pressure under Nitrogen
atmosphere protection. Subsequently, about 15-40% weight of NaHSO3 and cosolvent were introduced into
a four-necked flask (reaction kettle). The cosolvent was 20-50% of NaHSO3 aqueous solution. After being
stirred for 15 min, pMDI and solvent were introduced dropwise while stirring. During the whole procedure
of blocking reactions, stirring speed, loading speed, combined solvent, blocking temperature and time,
content of cosolvent, NaHSO3/NCO mole ratio, and initial NaHSO3 were the key parameters. The
temperature was constant at 0-2C, time for reaction was 1.5-6 hour, stirring speed was 150-500 rpm,
cosolvent were ethanol and water, solvent was 1,4-dioxane, NaHSO3/NCO mole ratio was 1.05-1.5. The
final blocked isocyanate was stored at room temperature. The storage period of blocked isocyanate was 30
days, pH was 4.8-5.5, and solid content was 28-35% (Zhang et al., 2011).

Deblocking reaction of sodium bisulphite-blocked polyisocyanate

The deblocking reaction of sodium bisulphite-blocked polyisocyanate was carried out using oven
attached to hermetic container. Deblocking experiment was carried out at different temperature of 70C,
80C, 100C (Zhang et al., 2011).

Characterisation
The deblocking temperature of blocked isocyanate was studied using DSC with a high pressure pot
under nitrogen atmosphere protection. The samples had of a mass of 3-8 mg were heated from 20 to 250C,
the heating rate was 5C/min. FTIR spectra of blocked and unblocked isocyanate adducts were recorded in
the range 400-4000 cm-1 at room temperature, in KBr pellets. TGA was performed from 30 to 600C at a
heating rate of 5C/min under nitrogen atmosphere protection with the gas flowing rate of 90 ml/min. The
samples had a mass of 5-10 mg.

Result and discussion

FTIR spectroscopy has been successfully employed to characterise blocked isocyanate adducts as
well as to measure their lowest deblocking temperature (Sankar and Nasar, 2006). FTIR spectra of blocked
isocyanate adducts is identical and shows no absorption in the 2250-2270 cm-1 range, which indicates that
the N=C=O group of the isocyanate molecules were completely blocked by sodium bisulphite. In this
experiment, blocked isocyanate and unblocked isocyanate were characterised by FTIR as shown in Figure 1.
In the spectra of unblocked isocyanate, the characteristic absorption peak of N=C=O around 2,264 cm-1
was in existence, which indicated the presence of free isocyanate groups. A characteristic absorption peak at
1732 cm-1 belonging to the C=O group was observed in the spectra of PMDI (Gao et al., 2005).

Figure 1. FTIR spectra of blocked and unblocked isocyanate

Peak of N=C=O
strecthing

Strong absorption peaks at 3401-3195 cm-1 (N-H stretching), 1,700 cm-1 (-C=O stretching of
urethane and carboxylic groups), 1521 cm-1 (N-H bending) confirmed the formation of urethane, which was
not urea that resulted by reaction of isocyanate and water. Comparing FTIR spectra of the unblocked
isocyanate with that of blocked, it was clearly from the spectra that chemical bonds of urethane formed
between sodium bisulphite and isocyanate. The absence of the N=C=O peak was due to the reactions with
sodium bisulphite. The method of blocking was feasible and the effect of blocking was effective. Therefore,
the preparation of the blocked isocyanate could be performed in water-based polymer system, in order to
avoid the reaction with water (Zhang et al., 2011).

Deblocking temperatures of the blocked isocyanate by sodium bisulphite

In order to study the regenerated activity of blocked isocyanate product, many analytical techniques
had been applied to study deblocking temperatures. DSC analysis was used to study the phase behaviour and
the deblocking temperature because the energy associated with deblocking of blocked isocyanate was quite
different with structure variations. Therefore, it should exhibit significant decalescence peak when they were
deblocked (Gedan-Smklka et al., 2000). DSC curve of blocked isocyanate solution with the optimum ratio
of NaHSO3 and NCO being 1.2 tested with high-press pans is shown in Figure 2. Deblocking temperature
was clearly observed from the absorption peak starting from 95.6 to 109.5C. This was due to the
decalescence peak of water or cosolvent, but the peak at 138.0C was the absorption peak of deblocking
temperature of blocked isocyanate (Zhang et al., 2011).
Figure 2. DSC curve of blocked isocyanate

It might be an obvious difference with the deblocking temperature of blocked isocyanate by sodium
bisulphite reported by the literature. The reason for this would be that the deblocking temperature of blocked
isocyanate is about 95C. However, decalescence peak of water and solvent were also at the same
temperature range, and they could overlap decalescence peak of free isocyanate. Moreover, a plenty of
solvent and water were used in the blocking reaction, they would influence the deblocking. But in the

temperature range from180 to 200C, free N=C=O functional groups of blocked isocyanate were generated
and self-crosslinked, which indicated that the blocking of isocyanate by sodium bisulphite was successful.
Also it could be seen from Figure 2 that the sharp endotherms peak of deblocking (190.8C) and exothermic
crosslinking (186C) for blocked isocyanate was obvious. Furthermore, this indicated that blocked
isocyanate had a very high performance and reactivity after deblocking. Therefore, the lowest deblocking
temperature of blocked isocyanate was 95C. The above studies have shown that blocked isocyanate could
be used at more than 95C in the curing system, such as preparing particleboards with UF resin (Zhang et
al., 2011). To confirm deblocking temperature, the blocked isocyanate was dried by means of low freezing
temperature and then tested by DSC analysis as Figure 3.
Figure 3. DSC curve of blocked isocyanate at optimum condition

The DSC curve in Figure 3 showed that the decalescence peak of blocked isocyanate at 72.6C was
due to being deblocked. Comparing with Figure 2, the decalescence peak began from 109.4C and then to
peak. It indicated that water and dioxane might influence the deblocking temperature of blocked isocyanate.
Therefore, in order to determine the deblocking temperature of the blocked isocyanate, it needed to be
extracted. Meanwhile it was also found that exothermic peak of DSC curve began from 170.6C. This was
clearly due to the self-crosslinking reaction of the deblocked N=C=O groups of blocked isocyanate.
Therefore, it could be determined that the blocked isocyanate could be deblocked to free N=C=O
functional groups via heating (Zhang et al., 2011).
The deblocking temperatures of the blocked isocyanates were determined with DSC and FTIR
analysis. The lowest temperature of absorption of the 2270 cm-1 in the 2260-2290 cm-1 range was detectable,
due to regeneration of the N=C=O group, and was noted as the lowest deblocking temperature. The
deblocking temperature of the blocked isocyanate in DSC spectra began from 70C. In Figure 4, the BPI
was the blocked isocyanate, and BPI07, BPI08, BPI10 were the blocked isocyanate baked at the different
temperatures of 70C, 80C and 100C in an oven for 30 min, and keep the blocked isocyanate in sealed
container. The FTIR spectra of BPI, BPI07, BPI08, BPI10 characteristic peaks were as the following: 3497-

3195 cm-1 (urethane N-H stretching), 2960-3000 cm-1 (aromatic ring =C-H stretching), 2300-2210 cm-1 (N=C=O stretching), 1732- 1690 cm-1 (urethane C=O stretching), 1520-1545 cm-1 (urethane N-H bending).

Figure 4. FTIR spectra of blocked polyisocyanate at different temperature

Peak of N=C=O
strecthing

In the spectra of BPI07, BPI08 and BPI10,as the temperature increasing, the intensity of N-H
stretching peak became more obviously. This might be due to that the regeneration of free N=C=O
functional groups of the blocked isocyanate generated dimer or tripolymer via the reaction of selfcrosslinking and curing. It could be concluded that FTIR analysis was an ideal analytical method to
investigate deblocking temperature of blocked isocyanate as it could measure the regeneration of the
N=C=O function group and the disappearance of the carbonyl group (C=O) of the blocked N=C=O group
(Zhang et al., 2011).
The results of TGA and DTG curves showed the thermal stability of the blocked isocyanate. In the
figure 5, four weight loss steps could be identified with the temperature ranges of 50-100C, 120C, 150200C and 250-350C. First, the decomposition temperature from 50 to 100C for 50 percent weight loss
was quite high as it was characteristic of small volatilizable molecule and blocked isocyanate. Second, the
blocked isocyanate showed a weight loss of only around 27 percent up to 120C. Third, the temperature
from 150 to 200C was traceable to the decomposition of the sodium bisulphite with releasing sulphur
dioxide, and the loss weight was 7 percent. The last step from 250 to 350C ascribed to the urethane bonds
and the loss weight was 10 percent. It confirmed the high thermal stability of self-crosslinking deblocked
isocyanate.

Figure 5. TGA curve

Figure 6. DTG curve

The deblocking temperatur of blocked isocyanate powder began from 80C and end at 151C, where 30 %
weight loss was observed (figure 6). When the temperature was approximately up to 150C, sodium
bisulphite began to decompose. Simultaneously, isocyanate also began to self-crosslink during the
temperatures range from150 to 250C. But the high thermal stability of self-crosslinking deblocked
isocyanate behaved during the temperature range from 250 to 450C (Zhang et al., 2011). There are also
steric effects on deblocking temperature. In one study, dimethyl ketoxime blocked TDI deblocked at 120C,
blocked MDI at 130C, blocked H12MDI at 136C, and IPDI adduct deblocked at 143C (Wicks and Wicks,
1999). A study of deblocking of a series of MEKO blocked isocyanates were evaluated for deblocking
temperature using TGA. In general, blocked aromatic isocyanates deblock at lower temperatures than
aliphatic isocyanates. This results from greater electron-withdrawing potensial of an aromatic ring as
compared to an aliphatic group (Wicks and Wicks, 1999).
Table 1 Deblocking temperatures of MEKO blocked monomeric isocyanates

Figure 7. Diisocyanate monomers-H6XDI, XDI, TMXDI.

Conclusions
Sodium bisulphite-blocked isocyanates with good solubility weresuccessfully synthesised with high
yield during the reaction of sodium bisulphite and isocyanate by the special procedure. The optimum
blocking conditions determined by blocking yield measurements was as follows: reaction time was 1.5-6 h,
reaction temperature was 0-25C, stirring speed was 150-500 rpm, cosolvent was ethanol and water, solvent
was 1,4-dioxane, NaHSO3/NCO mole ratio was 1.05-1.5.
Sodium bisulphite was a very efficient blocking agent for isocyanates at room temperature. The
higher reaction velocity of the sodium bisulphite was confirmed compared to the water because of the
presence of cosolvent and special method for dropwise due to the self-crosslinking reaction of the deblocked
N=C=O groups of blocked isocyanate. Therefore, it could be determined that the blocked isocyanate by
sodium bisulphite could be deblocked to free N=C=O functional groups via heating, and the deblocking
temperature of blocked isocyanates by sodium bisulphite was lower. The heating temperature was 95-105C,
blocked system could re-release isocyanate which could react with active hydrogen quickly and perform
isocyanate original effect. These results showed that sodium bisulphite was a very efficient blocking agent
for isocyanates.