BLOCKED AND DEBLOCKED

ISOCYANATE WITH NaHSO3

PREVIEW

What is an isocyanate?
Name : Methylene diphenyl diisocyanate (MDI)
Synonims : 4,4-Diphenylmethane diisocyanate, 1,1-Methylenebis,
Isonate, Hylene M50, Methylbisphenyl isocyanate.
Molecular formula : C15H10N2O2 (mw : 130 g/mole)
Chemical structure
The primary commercial form of MDI is
actually polymeric MDI (pMDI) which is a
mixture that contains 20-80% of 4,4-MDI
(Kapp, 2014).

One of wood adhesive with excellent bonding properties, water

resistance, aging resistance, no formaldehyde emission, and other
pollution problems (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).
Due to high reactivity of isocyanate group at room temperature, this
monomer is difficult to deposit for a long period (Lou and Di, 2013).

What is the solution????

ISOCYANATE BLOCKING TECHNOLOGY

Blocked isocyanate is a solution to overcome these drawbacks.
A blocked isocyanate is an adduct/product containing comparatively
weak bond formed by reaction between an isocyanate and a
compound contains 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).
Blocked isocyanates have wide spread use in many coatings areas:
automotive, maintenance, and industrial finishing (Wicks and Wicks,
2001).

ISOCYANATE BLOCKING TECHNOLOGY

The blocked isocyanate adhesive applied as wood adhesive should
be unblocked under less than 100C (Zhang et al., 2011)
Furthermore, blocked isocyanates are stable at room temperature in
the presence of polyols and water.
The overall reaction in the case of formation and hydrolysis of
blocked isocyanate can be seen at scheme 1, where NaHSO 3 was
the blocking agent (Wicks and Wicks 1999)

Scheme 1. Formation and hydrolysis reaction of bisulphite blocked isocyanate

Blocking Agent
As an abundant blocking agent, NaHSO3 has special properties such
as low unblocking temperature, low price, and no pollution.
Bisulphites 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.
Bisulphites blocked isocyanates are prepared by reacting
isocyanates in aqueous solutions of sodium bisulphite to give watersoluble 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).
Hydrolysis of bisulphite blocked isocyanate is pH dependent, being
slowest at low pH, blocked aromatic isocyanates undergo more rapid
hydrolysis than aliphatic isocyanates (Wicks and Wicks, 1999).

 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), thermo gravimetry 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 13C-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).

Experimental
Material

pMDI : Polymeric MDI

PEG
: Poly ethylene glycol
NaHSO3 : Sodium bisulphite as blocking agent
C2H5OH: Ethanol as cosolvent combine with water
1,4-dioxanel as solvent

Instrument

DSC
FTIR
TGA
13C-NMR
1
H-NMR

to analyze deblocking temperature

to characterise unblocked and blocked isocyanate
to investigate deblocking reaction
to track the intensity of C and H atoms within
blocking group, which more intense after deblocking
Depend on blocking agent

Method
Preparation of blocked isocyanate (Zhang et al., 2011).
1000 mL flask was refrigated at the temperature of 0-25C with a
pressure under Nitrogen atmosphere protection
15-40% of NaHSO3 and cosolvent (20-50% of NaHSO3 aqueous
solution) were introduced into a four-necked flask (reaction kettle)
stirred for 15 min
pMDI and solvent (1,4-dioxane) were introduced dropwise while
stirring
The temperature was maintained at 0-2C, time for reaction was 1.56 hour, stirring speed was 150-500 rpm, NaHSO 3/NCO mole ratio
was 1.05-1.5

Deblocking reaction of sodium bisulphite-blocked

polyisocyanate (Zhang et al., 2011).
The deblocking reaction was carried out using oven attached to
hermetic container at different temperature of 70C, 80C, 100C for
30 min

Characterisation (Zhang et al., 2011).

Deblocking temperature of blocked isocyanate was studied using

DSC with a high pressure under nitrogen atmosphere protection. The
samples had of 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.

 FTIR spectroscopy: FTIR was used to examine chemical structure of blocked

isocyanate. The FTIR spectra were recorded with a spectral range of 4000
400 cm-1.
DSC measurement: To examine the thermal behavior of blocked isocyanate,
was scanned at a heating rate of 10C/min, with a temperature range of 20
300C.
NMR: 1H NMR and 13C NMR spectra were recorded in dimethyl sulfoxide
(DMSO) on a Bruker AV400 spectrometer (Bruker Daltonic Inc., USA),
working at 400.13 and 100.61 MHz, respectively.
Particle size: Particle size was measured, using a LS-800 laser particle sizer
(Omec-instruments, China). SEM: The SEM measurements were analyzed
using Hitachi S-3400 scanning electron microscope (SEM) (Hitachi Limited,
Japan). The cryogenically fractured surfaces were etched with chloroform for
24 h to remove the thermoplastic phase. The specimens were dried in
vacuum overnight to remove the solvent. All the specimens were sputter
coated with gold before taking the micrographs.
(Lou and Di, 2013)

Result
In this experiment, blocked isocyanate and unblocked isocyanate
were characterised by FTIR as shown in Figure 1.

Result
Deblocking temperatures of the blocked isocyanate by sodium
bisulphite
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

Result
The deblocking temperatures of the blocked isocyanates were determined
with DSC and FTIR analysis.
BPI7 :
deblocked at
70C
BPI8 :
deblocked at
90C
BPI10 : deblocked
at 100C

Result
The results of TGA and DTG curves showed the thermal stability of the
blocked isocyanate

Conclusions
Sodium bisulphite-blocked isocyanates with good solubility were
successfully 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 hour, 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 1.051.5.

Other method (EP0929518 A1)

Blocked TMXDI was prepared in the followin:
Sodium metabisulphite (190 g) was dissolved in 530 g of water. The
clear solution obtained was placed in a flask provided with a stirrer
and cooling means.
l-Methyl-2-pyrroIidinone (200g) was added to the solution along with
120g of m-tetramethylxylene di-isocyanate. 3.5g of triethanolamine
and 0.1 g of dibutyl tin dichloride. The mixture was maintained at 5
degrees Celsius with continued stirring for seven days at which time
the reaction mixture had become one aqueous suspension. After
filtering this mixture, the residue contained the desired blocked
isocyanate and the filtrate, after evaporating and adding excess
acetone yielded a further crop of blocked isocyanate. The combined
yield was 180g of the sodium salt of the blocked isocyanate.

What we are going to do?

Trying to prepare of bisulphite blocked isocyanate with mole ratio of
NaHSO3/NCO = 1.2, 1.4, 1.6, 1.8, 2.0 (max 2.0)
15-40% of NaHSO3 and cosolvent (20-50% of NaHSO3 aqueous solution) were
introduced into a four-necked flask (reaction kettle) stirred for 15 min
The temperature was maintained at 5-15C, time for reaction was 1.5-6 hour,
stirring speed was 150-500 rpm, NaHSO3/NCO mole ratio was 1.2-2.0
Deblocking temperature of blocked isocyanate was studied using DSC with a high
pressure under nitrogen atmosphere protection. The samples had of 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.