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Quantitative determination of primary aromatic amines in recycled cold-cure and flexible foams

Application No.: VCH0015 
Version 1  02/2018

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Quantitative determination of primary aromatic amines in recycled cold-cure and flexible foams

Juliane Böttcher, Kate Monks; applications@knauer.net
KNAUER Wissenschaftliche Geräte GmbH, Hegauer Weg 38, 14163 Berlin

Quantitative determination of primary aromatic amines in recycled cold-cure and flexible foams

Summary

A reliable method for the quantification of aryl amines in cold-cure and flexible foams from recycled mattresses is described in the following application. The focus was set on two substances, 2,4-diaminotoluene (TDA) and 4,4-diaminodiphenylmethane (DAPM), which are mandatory to be determined before processing the recycled foam due to their carcinogenic properties.

Introduction

Cold-cure and flexible foams used for the production of mattresses are made of polyurethane synthetics. During the synthesis of urethanes, which are the basis for polyurethanes, different intermediate products are formed. Two of these products occurring in the process are DAPM and TDA. Both substances are classified as carcinogenic. Furthermore TDA is presumed to be teratogenic and mutagenic. When recycling the cold-cured and flexible foams it i s necessary to determine the concentration of these compounds before reusing the foams. Referring to OEKO-TEX® Standard 100 a limit value of 20 mg/kg for aryl amines is appointed [1].

2,4-Diaminotoluene

2,4-Diaminotoluene

4,4-Diaminodiphenylmethane

4,4-Diaminodiphenylmethane

Results

For the quantification a calibration was made. Therefore a mixed standard of DAPM and TDA at five different concentrations was used. For both components a correlation coefficient of R2 = 0.999 was achieved. Exemplary one sample of flexible foam was selected and spiked with standard to a concentration of 0.1 mg/mL. Fig 1 shows the sample measurement and Fig 2 shows an overlay of the sample (red) and spiked sample (blue) of flexible foam. The limit of detection (LOD) was determined with 0.63 µg/mL for TDA and 0.67 µg/mL for DAPM.

Fig. 1 Sample of flexible foam (18 mg/mL)

Fig. 1 Sample of flexible foam (18 mg/mL)

Fig. 2 Overlay of sample (red) and spiked sample (blue) of flexible foam

Fig. 2 Overlay of sample (red) and spiked sample (blue) of flexible foam

Materials and Methods

An AZURA® Analytical HPLC Plus system for a pressure range up to 700 bar was used for this application. It consisted of an AZURA P 6.1L LPG pump, an autosampler 3950, an AZURA CT 2.1 column thermostat and an AZURA MWD 2.1L multiwavelength detector. The analytical method was run with a step gradient at a flow rate of 1.0 mL/min. The mobile phase was a mixture of water and acetonitrile, both with 0.1 % triethylamine as mobile phase modifier. The column thermostat was set to 25 °C and the detector recorded at 290 nm. The column that was used was filled with ProntoSIL 120-3 C8 ace EPS silica.

Conclusion

With the developed method and the AZURA HPLC Plus system it was possible to perform a rapid quantitative analysis of 2,4-diaminotoluene and 4,4-diaminodiphenylmethane without time consuming sample preparation. Even a complex matrix such as the recycled cold-cured and flexible foams can be determined robust and reproducible with the specified method parameters.

Additional Results

Fig. A1 Mixed standard of TDA and DAPM (both 0.1mg/mL)

Fig. A1 Mixed standard of TDA and DAPM (both 0.1mg/mL)

Additional Materials and Methods

Tab. A1 Method parameters

Eluent A

H2Odd + 0.1 % TEA

Eluent B

Acetonitrile + 0.1 % TEA

Gradient

Time [min]

% A

% B

0

95

5

5

95

5

15

35

65

15.02

0

100

25

0

100

25.02

95

5

35

95

5

Flow rate

1 mL/min

System pressure

ca. 190 bar

Column temperature

25 °C

Run time

35 min

Injection volume

10 µL

Injection mode

Full loop

Detection wavelength

290 nm

Data rate

20 Hz

Time constant

0.05 sec

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Tab. A2 System configuration & data

Instrument

Description

Article No.

Pump

AZURA® P 6.1L LPG, 10 mL, SSt

APH35EA

Autosampler

Autosampler 3950

A50070

UV Detector

AZURA® MWD 2.1L

ADB01

Flow cell

LightGuide 10 mm, 2 µL

AMC19

Thermostat

AZURA® CT 2.1

A05852

Eluent tray

AZURA® E 2.1L

AZC00

Column

Vertex Plus Column 150 x 4.6 mm ProntoSIL 120-3 C8 ace EPS with precolumn

15VF08APSG

Software

OpenLAB CDS EZChrom Edition

A2600-1

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KNAUER System Configuration

References

[1] https://www.oeko-tex.com/de

Related KNAUER Applications

VCH0016 – Determination and quantification of acrylic acid derivatives

Application details

Method

HPLC

Mode

RP

Substances

2,4-diaminotoluene, 4,4-diaminodiphenylmethane

CAS number

95-80-7, 101-77-9

Version

Application No.: VCH0015 | Version 1 02/2018 | © KNAUER Wissenschaftliche Geräte GmbH

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