Analysis of Polymer Additives Using the LCMS-8030 Triple - Shimadzu

LAAN-A-LM-E050
Liquid Chromatography Mass Spectrometry
No.C79
Analysis of Polymer Additives Using the LCMS-8030 Triple Quadrupole LC/MS/MS
Antioxidants, ultraviolet absorbers, flame retardants
and other polymer additives are indispensable for
improving the characteristics and functionality of
polymers. Understanding the types and quantities of
these additives to be used is extremely important to
effectively control the manufacturing process of the
polymers.
Below is an example of quantitative analysis of 14
types of polymer additives using MRM (Multiple
Reaction Monitoring) and the LCMS-8030 triple
quadrupole mass spectrometer.
n MRM Analysis with the LCMS-8030
Conducting MRM measurement with a triple quadrupole
mass spectrometer makes it possible to obtain
molecular structure information while simultaneously
performing quantitative analysis. Fig. 1 shows the
chromatograms of 14 polymer additives. Two additives
were analyzed in positive mode, and 12 were
analyzed in negative mode. Fig. 2 shows the calibration
curves of each of the constituents. Excellent linearity
was obtained for every compound tested.
(×10,000,000)
1.25
1.00
0.75
0.50
0.25
0.00
Irganox 245 585.30>367.20(-)
Irganox MD 1024 551.35>333.40(-)
Irganox 1098 635.45>417.50(-)
Tinuvin P 226.10>107.10(+)
Cyanox 2246 339.15>163.20(-)
Cyanox425 367.25>177.20(-)
Irganox 1035 641.35>83.20(-)
Irgafos 168 oxide 663.50>57.15(+)
Tinuvin 120 437.25>205.25(-)
Irganox 1010 1175.70>1175.70(-)
Tinuvin 328 350.25>319.85(-)
Irganox 1330 773.55>773.55(-)
Irganox 565 587.35>58.10(-)
Irganox 1076 529.45>41.15(-)
2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 min
Fig. 1 Chromatograms of 14 Polymer Additives
3.0
2.5
(×100,000)
Irganox 245
1-500 ppb
2.25
2.00
1.75
Irganox MD 1024
(×100,000)
1-1000 ppb
1.00
Irganox 1098 Tinuvin P Cyanox 2246
(×100,000) (×100,000) (×1,000,000)
5-500 ppb
2.5
2.0
1-1000 ppb
3.5
3.0
0.01-100 ppb
2.0
1.5
1.0
0.5
0.0
R^2=0.995
0 100 200 300 400
1.50
1.25
1.00
0.75
0.50
0.25
R^2=0.997
0.75
2.5
1.5
2.0
0.50
1.0
1.5
1.0
0.25
0.5
0.5
R^2=0.996 R^2=0.999 R^2=0.997
0.00
0.00
0.0
0 250 500 750
0 100 200 300 400
0 250 500 750
0.0 25.0 50.0 75.0
3.0
2.5
2.0
1.5
1.0
0.5
(×1,000,000)
Cyanox 425 Irganox 1035 Irgafos 168 oxide Tinuvin 120 Irganox 1010
0.01-100 ppb
0.0
0.0 25.0 50.0 75.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
(×10,000)
0.5-100 ppb
5.0
4.0
3.0
2.0
1.0
(×10,000) (×1,000,000) (×10,000)
5-500 ppb
0.01-100 ppb
0.1-100 ppb
1.0
R^2=0.997 R^2=0.998 R^2=0.996 R^2=0.997 R^2=0.997
0.0
0.00
0.0
0 100 200 300 400 0.0 25.0 50.0 75.0
0.0 25.0 50.0 75.0
1.75
1.50
1.25
1.00
0.75
0.50
0.25
6.0
5.0
4.0
3.0
2.0
1.0
0.0
0.0 25.0 50.0 75.0
1.25
1.00
0.75
0.50
0.25
(×100,000)
Tinuvin 328 Irganox 1330
500-10000 ppb
R^2=0.999
(×1,000,000)
0.5-10000 ppb
R^2=0.998
0.00
0.0
0 2500 5000 7500 0 2500 5000 7500
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
1.00
0.75
0.50
0.25
(×1,000,000)
Irganox 565
0.5-500 ppb
R^2=0.996
0.00
0 100 200 300 400
3.5
3.0
2.5
2.0
1.5
1.0
0.5
(×100,000)
Irganox 1076
1-1000 ppb
R^2=0.999
0.0
0 250 500 750
Fig. 2 Calibration Curves of 14 Polymer Additives

No.C79
n Analysis of Unknown Polymer Additives Using the LCMS-8030
Quantitative analysis was conducted for the polymer chromatograms of the substances detected. The
additives in a food wrapping material and food concentrations of each of the constituents calculated
container. THF (1 mL) was added to a pulverized using the calibration curves of Fig. 2 were determined
sample (0.1 g), and this was sonicated for 1 minute. to be 49.4 ng/g of Irganox 1010 detected in the food
The supernatant was collected, 1 mL of 5 mM wrapping material, and 14.3 μg/g of the Irganox 245
ammonium acetate was added, and the final mixture and 48.7 ng/g of Irganox 1010 detected in the food
was filtered (0.45 μm.)
container.
Fig. 3 shows the MS chromatograms and the MRM
(×10,000)
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
Food Wrapping Material
(×100,000)
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
Food Container
2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 min 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 min
2.5
2.0
(×1,000) (×100,000) (×1,000)
1.2
1.5
1.0
4.859
3.258
4.863
1.5
1.0
0.8
1.0
0.5
49.7 ng/g 14.3 μg/g 0.6
0.5
48.7 ng/g
0.4
0.0
4.7 4.8 4.9 5.0
0.0
3.1 3.2 3.3 3.4
0.2
4.7 4.8 4.9 5.0
Irganox 1010
Irganox 245 Irganox 1010
Fig. 3 Chromatograms of Polymer Additives Detected in the Analysis
(Left) Food Wrapping Material, (Right) Food Container
Table 1 Analytical Conditions
Column
: Shim-pack XR-ODS (75 mmL. × 2.0 mmI.D., 2.2 μm)
Mobile Phase A : 0.1 % formic acid
Mobile Phase B : Methanol
Gradient Program : 25 %B (0 min) - 100 %B (2.5-7.5 min) - 25 %B (7.51-10 min)
Flow Rate
: 0.5 mL/min
Injection Volume : 2 μL
Column Temperature : 40 °C
MS
Probe Voltage
Nebulizing Gas Flow : 1.5 L/min
Drying Gas Pressure : 10 L/min
DL Temperature : 250 °C
BH Temperature : 400 °C
: SHIMADZU LCMS-8030
: +4.5 kV (ESI-Positive mode),
–3.5 kV (ESI-Negative mode)
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