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Quantification Of 2,4 And 2,6 Isomers Of Toluene Diisocyanate By Gas

Chromatography
S.S. Mhase*, A.P.Singh ,Dr(Mrs) N.Sikder , Dr.S.N.Asthana.
High Energy Materials Research Laboratory , Sutarwadi, Pune-411021
ssmhemrl@rediffmail.com

Abstract
Technical grade Toluene Diisocyanate (TDI) is a mixture of 2,4 and 2, 6 isomers
approximately in 80 : 20 or 65: 35 ratio. Mechanical properties of cured polymer depend
upon the ratio of the two isomers, hence as quality control requirement , their exact ratio
must be known. Conventional method being functional groups dependent, limits its
application for analysis of positional isomeric compounds such as 2,4 and 2,6 TDI . In
such cases instrumental methods of analysis like High Performance Liquid
Chromatography( HPLC), Gas Chromatography (GC) ,Fourier Transformed Infra Red
spectroscopy ( FTIR) and Nuclear Magnetic Resonance spectroscopy (NMR) are ideal
choice. The GC method has been established for the quantification of the isomers. This
paper deals with development of GC condition using megabore capillary column for
optimum separation of the 2,4 ,2,6 isomers of the TDI and impurities associated with it,
followed by their quantification using area normalization. The method established for
quantification of the 2,4 and 2,6 isomers of TDI by gas chromatography using area
normalization is fast, accurate, precise , cost effective and easily accessible. The
accuracy of the method is 96 % and 90 % for 2,4 isomer and 2,6 TDI respectively.

1.Introduction

Toluene diisocynate ( TDI) is one of the curing agents for polyurethane polymers.
Technical grade TDI is a mixture of 2,4 and 2, 6 isomers approximately in 80 : 20 or 65:
35 ratio(1) . Mechanical properties of cured polymer depend upon the ratio of the two
isomers, hence as quality control requirement, their exact ratio must be known.
Conventional method being functional groups dependent, limits its application for
analysis of positional isomeric compounds such as 2,4 and 2,6 TDI 2 . In such cases
instrumental methods of analysis like High Performance Liquid Chromatography
3
( HPLC) , Gas Chromatography (GC)4,5,6 , FTIR7 and NMR8 are ideal choice. The
HPLC and GC separate the components of mixture on the basis of solubility, partition and
adsorption, followed by its detection with suitable detectors. The NMR identifies the
isomers due to different environment of the functional group while FTIR method is
based on the absorption peaks due to out of plane C-H deformation vibration at
12.35μm and 12.80 μm for 2,4 and 2,6 TDI respectively. Quantitative analysis by FTIR is
time consuming while NMR is expensive and not easily accessible. The HPLC is used
for trace level analysis of TDI that too with derivatisation. Analysis of TDI isomers by GC
is reported, however , the details are not available. Moreover, manufacturers also report
isomer ratio by area normalization using GC analysis9 .Hence, GC method is established
for the quantification of 2,4 and 2,6 isomers of TDI.
2. Experimentation
2.1 Materials
2.1.1 Chemicals
Technical grade 80:20 TDI from Bayer, BASF and Across while standard 2,4 and
2,6 TDI from Sigma ( purity ≥ 98%) and Aldrich (97%) respectively were used.
2.1.2 Solvents
AR grade toluene having purity more than 99 % was used.
2.2 Equipments
2.2.1 Gas Chromatograph
Nucon make indigenous Gas Chromatograph having split less flash injector , mega
bore column and Flame Ionization Detector (FID) was used.
2.3 Sample Preparation
The TDI being very reactive to active hydrogen , toluene , an aprotic solvent was
used for solution preparation.
2.4 Experimental details
Initially GC condition ( Injector: 210°C, Oven : 60°C- 2 min @8°C -190°C @ 25°C-
230°C,Detector-FID(250°C),Column:DB-17, L-30 M,ID-0.53mm, Film-1.0 m, Nitrogen
as carrier gas, Flow-2 cm3 /min and makeup – 30 cm3 / min ) was established for optimum
resolution of 2,4 and 2,6, TDI isomers. Technical grade ( 80:20) TDI from Bayer,
BASF and Across were analyzed under the same conditions to confirm the presence of
2,4 and 2,6 isomers by matching the Retention Time (RT) with standard 2,4 and 2,6
isomers and to resolve the impurities present therein. The chromatograms were recorded
using Iris32 data acquisition system. Further, confirmation of the isomers and impurities
was done by GC-MS10.
The 2,4 and 2,6 TDI being positional isomers , their expected equal response to the
FID was checked by determining sensitivity and linearity at the established GC
condition. The sensitivity and linearity were determined by plotting response of 2,4 &
2,6 TDI against concentrations . As the sensitivity of both the isomers was found to be
same, quantification of the isomers of technical grade (80:20) TDI from Bayer, BASF and
Across was carried out by area normalization where area under the peak is directly
proportional to percentage of the isomers.
The validation of the method was carried out by estimation of the mixture made from
standard 2,4 and 2,6 isomers in 80.55 : 19.45 ratio. The analysis was carried out in
triplicate to calculate % RSD.
3. Results and Discussions
The GC Chromatograms for isomers and their mixtures shows well resolved peaks
(Figure 1- 4) .The GC chromatogram of standard 2,4 TDI (Figure 1) shows two peaks
while 2,6 TDI (Figure 2) shows three peaks. Apart from the major peak of respective
TDI isomer , other peaks were confirmed as isomers of TDI and impurity (2H-
Benzimidazol-2-one, 1, 3-dihydro-5-methyl-) by GC-MS .

2,4 TDI
2,6 TDI

2,6 TDI
Impurity Isomer of TDI
Impurity

Figure 1 GC chromatogram for Figure 2 GC chromatogram of standard


standard 2,4 TDI 2,6 TDI
The GC chromatogram of the technical grade (80:20) TDI from Bayer, BASF and
Across ( Figure 3 ) shows four compounds eluting at 15.68, 15.89, 16.13 and 18.05 RT
indicating that the technical grade TDI is a mixture of four components. The RT of these
compounds match with the compound present in standard 2,4 and 2, 6 TDI.

2,4 TDI 2,4 TDI

2,6 TDI
2,6 TDI

Impurity
Isomer of TDI Impurity Isomer of TDI

Figure 3 GC chromatogram of technical Figure 4 GC chromatogram of


grade (80:20) TDI from Across 80.55:19.45 standard TDI

The technical grade TDI was also analyzed by GC-MS ( Figure 5(a)- 5(i)) and the
compounds were confirmed as isomers of TDI and impurity (2H-Benzimidazol-2-one, 1,
3-dihydro-5-methyl-).

2,4 TDI
(19.2 min) 2,6 TDI
(19.3 min)

Isomer of TDI
Impurity

Figure 5 (a) GC-Chromatogram of GC- Figure 5 (b) MS of compound eluted


MS for Technical Grade (80:20) TDI at 19.2 min
Figure 5 (c) Library match for compound Figure 5 (d) MS of compound eluted
eluted at 19.2 min at 19.3 min

Figure 5 (e) Library match for compound Figure 5 (f) MS of compound eluted
eluted at 19.3 min at 19.53 min

Figure 5(g) Library match for of Figure 5 (h) MS of compound eluted at


compound eluted at 19.53min 21.2
Figure 5 (i) Library match for compound eluted at 21.2 min

3.1 Quantification by area normalization


The response of 2,4 and 2,6 isomers are nearly same under given range of linearity
(Figure 6).

1000
Calibration curves for 2,4 and 2,6 TDI
900

800 y = 10194x
R 2,4 TDI
R² = 0.998
E 700 2,6TDI

S
600
P
O 500
N 400 y = 10552x
S R² = 0.999
E 300

200
m
V 100

0
0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.1

Weight (g)
Figure 6 calibration curves for 2,4 and 2,6 TDI

Hence, the area under peaks of 2,4 and 2,6 isomers of technical grade TDI is
proportional to their concentration. The concentration of the 2,4 and 2,6 isomers of TDI
from Bayer, BASF and Across ( Table 1 ) are not in the ratio of 80: 20.
Table 1 Gas chromatographic analysis results of technical grade (80:20) TDI and
Standard 2,4 and 2,6 TDI by area normalization.

S.No Source Technical grade (80:20) TDI


2,4 2,6 TDI TDI isomer(%) Impurity (%)
TDI(%) (%)
1 Bayer 76.40 22.30 0.70 0.60
2 BASF 75.60 22.70 0.70 1.10
3 Across 76.70 21.70 0.70 0.90
4 Standard 2,4 TDI
Sigma ( ≥ 98%) 98.3 0.8 --- 0.9
5 Standard 2,6 TDI
Aldrich (97%) -- 98.0 1.00 1.00
6 TDI ( 77.70 21.50 0.30 0.50
80.73:19.26)

The deviation from 80: 20 ratio is due to the fact that the ratio mentioned by the
manufacturer is an approximate value 80:20 , secondly in addition to the 2,4 and 2,6 TDI ,
there are two more impurities in the technical grade TDI. The % RSD which is a measure
of precision , depends upon the concentration of the ingredients. It is found to be 2%
and is well within the accepted limits of analytical method.
3.2 Validation of the method
The validation of the method has been carried out by estimating the 2,4 and 2,6
isomers ratio in mixture of TDI made from stdandard 2,4 and 2,6 TDI . The accuracy of
the method is found to be 96% and 90 % for 2,4 and 2,6 TDI isomer respectively which
is well within accepted limits of analytical method.
4. Conclusion
The method established for estimation of the 2,4 and 2,6 isomers of TDI by gas
chromatography using area normalization is fast, accurate, precise , cost effective and
easily accessible. The accuracy of the method is 96 % and 90 % for 2,4 isomer and 2,6
TDI respectively.
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