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Study on The Deblocking

Reaction of Blocked pMDI

• Many analytical techniques have been applied to studying the reactions of
blocked isocyanates.
• One needs to remember that reported deblocking temperature frequently
depend on the method of analysis, heating rate, chemical structure of
blocking agent, chemical structure of isocyanate monomer, and other
variables.
• Different analytical techniques can give different deblocking temperature for
the same sample.
• (Wicks and Wicks, 1999)

Thermogravimetry Analysis
1. The thermal stability was investigated using a TGA 209 F3 thermal analysis
system (NETZSCH Co. Germany). Approximately 5 mg of sample was
scanned from 30 to 700°C at a heating rate of 10°C/ minute in an argon
atmosphere at a flow rate of 30 ml/minute. The TGA and derivative
thermogravimetric (DTG) curves were tested by TGA209F3 instrument
(Zhang, et al., 2014).
2. Thermogravimetric analyses were performed on a Perkin-Elmer TGA7
series. The measurements were performed in a nitrogen atmosphere with a
heating rate of 20°C/min (Mohammed and Sankar, 2011).
3. TGA was performed from 30 to 600°C at a heating rate of 5°C/min under
nitrogen atmosphere protection with the gas flowing rate of 90 ml/min. The
samples had a mass of 5-10 mg (Zhang, et al., 2011).

Differential Scanning Calorimetry
1. Differential scanning calorimetry DSC analysis of the blocked polyurethane
was performed on a NETZSCH D204 DSC, and argon at a flow rate of 30
ml/ minute was used as the purge gas. The scanning temperature ranged
from 30 to 200°C at a heating rate of 5°C/minute (Zhang, et al., 2014).
2. Differential scanning calorimetric (DSC) analyses were performed on a
Perkin-Elmer DSC7 series in a nitrogen atmosphere. A heating rate of
10°C/min was applied (Mohammed and Sankar, 2011).
3. The samples had of a mass of 3-8 mg were heated from 20 to 250°C, the
heating rate was 5°C/min, under nitrogen atmosphere (Zhang, et al., 2011).

Deblocking temperature from
aromatic isocyanate
Monomer of Isocyanate

Blocking Agent

Deblocking T(°C)

MDI

MEKO

90-180

MDI

Caprolactam

110-180

MDI

DPMA

75-125

MDI

NaHSO3

90-105

TDI

MEKO

70-150

TDI

Caprolactam

110-180

TDI

DPMA

-

Subramani et al., 2003)

Important Note
• Sample Preparation
• It is very important to ensure that the sample is in intimate contact with the
bottom of the crucible.
• It is important to have an accurate measure of the sample weight,
because the accuracy of the heat of reaction measurement is only as
good as the weight measurement. Recommended sample weights are
between 5 and 20 mg.
(Hale, 2002)

Important Note
• Initial Temperature
– The selection of the initial temperature obviously depends on the
temperature at which the thermoset starts reacting. If the system reacts at
room temperature, then some information will be lost.
– It is preferable to start the run at least 20°C until 40°C below the expected
onset of the reaction.
(Hale, 2002)

Important Note
• Final temperature
• Final temperature should be high enough to allow the reaction to go to
completion.
• Ideally, final temperature will allow full development of the exotherm curve
and a flat baseline at the end of the run.
Example:
Epoxies can typically be scanned up to 250-275°C, but Urethanes and
isocyanate group scanned lower than that.
(Hale, 2002)

Important Note
• Heating Rate
– It is common to employ heating rates between 5 and 20°C/min.
– If the heating rate is too fast, there may not be enough time for the
reaction to proceed to completion.
– If the heating rate is too slow, the signal may be too low for the instrument
to detect the heat.
– The most accurate way to select the appropriate heating rate is to run
several samples at different heating rates.
(Hale, 2002)

SUMMARY
• Differential scanning calorimetry (DSC) analysis:
• 5 mg of blocked pMDI were heated from 20 to 200°C, with heating rate
10°C/min under nitrogen atmosphere.
• Differential scanning calorimetry (DSC) analysis:
• 5-10 mg of blocked pMDI were heated from 20 to 600°C, with heating rate
10°C/min under nitrogen atmosphere at a flow rate of 30 ml/minute.

References
• Hale, A. (2002). Thermosets. Handbook of Thermal Analysis and Calorimetry Vol. 3, 3, 295–
354.
• Mohammed, I. A., & Sankar, G. (2011). Synthesis, deblocking and cure reaction studies of
secondary alcohol-blocked isocyanates. High Performance Polymers, 23, 535–541.
• Subramani, S., Park, Y. J., Lee, Y. S., & Kim, J. H. (2003). New development of polyurethane
dispersion derived from blocked aromatic diisocyanate. Progress in Organic Coatings, 48,
71–79.
• Wicks, D. A., & Wicks, Z. W. (1999). Blocked isocyanates III: Part A. Mechanisms and
chemistry. Progress in Organic Coatings, 36, 148–172.
• Zhang, Y., Gu, J., Jiang, X., Zhu, L., & Tan, H. (2011). Investigation on blocking and
deblocking isocyanates by sodium bisulphite. Pigment & Resin Technology, 40, 379–385.
• Zhang, Y., Cao, J., Tan, H., & Gu, J. (2014). New thermal deblocking characterisation method
of aqueous blocked polyurethane. Pigment & Resin Technology, 43, 194–200.