Toluenediamine in polyurethane foams

Hazard or artefact?
K. Hall, F. A. L. van Parys, and R. J. Young
The aim of this study was to investigate the formation of the suspected
carcinogen toluenediamine (TDA) as a degradation product of polyurethane.
For this purpose, a series of model systems was prepared, including linear
polyurethanes and foams. The starting materials were fully characterised using
melting point and refractive index determination, end group analysis, infra-
red spectroscopy, nuclear magnetic resonance spectroscopy and coupled gas
chromatographymass spectrometry (GCMS). A model commercial poly-
urethane foam was also prepared. Three dierent solvent extraction protocols
were applied and the extracts analysed by coupled GCMS and high per-
formance liquid chromatographymass spectrometry. No detectable amounts
of TDA could be found in extracts of both linear polyurethane and foam
incubated using either toluene or 1% acetic acid solution. By contrast, TDA
was found in extracts from both linear polyurethane and foam that had been
exposed to alkaline conditions during the extraction procedure. These ndings
conrm that the formation of TDA in extraction and GCMS analysis of
polyurethane samples results from hydrolytic degradation processes of poly-
urethane and that alkaline conditions should be avoided during extraction
and analysis. PRC/1753
2001 IoM Communications Ltd. Mr Hall is with Hall Analytical
Laboratories Limited, Floats Road, Manchester, M23 9YJ, UK and Mr van
Parys and Professor Young are at the Materials Science Centre, UMIST/
University of Manchester, Grosvenor Street, Manchester, M1 7HS, UK.
Manuscript received 13 August 2001; accepted in nal form 8 October 2001.
INTRODUCTION by the heat generated in the exothemic urethane form-
ing reaction and is trapped in the reaction mixture Polymeric materials such as polyurethanes are replacing
traditional materials in several applications but, like when the viscosity of the latter increases rapidly as
polymerisation proceeds. Chlorouorocarbons were any material, are subject to degradation. In addition
to mechanical failure of the material, degradation can widely used for this purpose prior to the Montreal
Protocol. The addition of water results in reaction have another eect: hazardous chemical degradation
products may be released and pose a threat to health. with some of the diisocyanate generating carbon
dioxide that acts as blowing agent as shown in Fig. 1. The development of valid protocols for the measure-
ment of such materials is the subject of this article.
A polyurethane is formed when a di- or polyiso-
cyanate and a polyol are made to react in the presence BACKGROUND
There are many aspects to degradation of materials of suitable catalysts and additives. Most polyurethanes
are based on two types of diisocyanates: toluene diiso- including polymers and these lead to a variety of
consequences such as a deterioration in mechanical cyanate (TDI) and diphenylmethane diisocyanate
(MDI) and their derivatives. The most widely used is properties, changes in colour and appearance, and the
release of hazardous chemical products. In particular, TDI as an 80:20 mixture of the 2,4 and 2,6 isomers.
Whereas there are only a limited number of types of the hydrolytic degradation of polyurethanes can lead
to the formation of carbamic acids that are unstable isocyanates used, a variety of polyols are available
to produce polyurethanes; these are generally either and eliminate carbon dioxide to form the amino
analogue of the starting isocyanate. Temperature is polyester based or polyether based polyols.
The properties of the polyurethanes obtained are an important environmental inuence on hydrolysis.1
The same amine is also formed from the isocyanate controlled largely by two main factors: the molar
mass of the polyols and their functionality. Polyols when water is used to generate the blowing agent.
In the case of TDI based polyurethanes, the used to make exible foams have a high molecular
mass and a rather low functionality (usually ~3), amine involved is toluenediamine (TDA). 2,4-Toluene-
diamine has been assigned the code R45 (may cause providing long chains between the junction points
and as such producing a exible network polymer. cancer).2 The reported nding of TDA in polyurethane
degradation products is therefore of major importance When producing foams, a blowing agent may be used.
This is a low molecular substance, which evaporates in relation to environmental health. Swedish scientists
C N O
H
2O
H
2 +
CO
2
Ar
Ar H C N
H O
O
N Ar
1 Reaction of diisocyanate with water, generating carbon dioxide
426 Plastics, Rubber and Composites 2001 Vol. 30 No. 9 ISSN 14658011
Hall et al. Toluenediamine in polyurethane foams 427
tda 10ppm
8.00 9.00 10.00 11.00 12.00 13.00 14.00
Time 0
100
%
10ppm Scan EI+
TIC
8.90e6
10.35
(a)
(b)
2 a Total ion chromatogram for GCMS of TDA standard sample (10 ppm); b mass spectrum and library
example of standard TDA corresponding to peak at R
t
=1035min in a
found TDA in urine and plasma from workers exposed system is that only the two basic reactants are present,
leaving out the possible inuence of additives and to thermal degradation products of TDI based poly-
urethanes.35 The study was performed at a factory simplifying the situation.
where workers were heating TDI based polyurethane
and thermal degradation compounds such as iso-
cyanates, aminoisocyanates, and amines were released. EXPERIMENTAL
The reactants were characterised fully by use of The presence of TDA in urine and serum samples
from women with polyurethane covered silicone refractometry, coupled gas chromatographymass
spectrometry (GCMS), infrared (IR), and nuclear breast implants, resulting from biodegradation of the
polyesterurethane foam has also been reported.68 magnetic resonance (NMR) spectroscopy. In particular,
the absence of TDA in any of the reactants was clearly In addition TDA has been found after chromato-
graphic analysis of extracts of model foams.9 However demonstrated. All reactants, with the exception of
the polyol, were supplied by Sigma-Aldrich Co. Ltd, the belief has grown that this nding depends on
the method used to extract the TDA. The experi- Dorset, UK. Two forms of TDI were used. One was
the pure 2,4 isomer and the other an 80:20 mixture mental conditions during extraction of polyurethane
samples are thought to generate TDA by hydrolysis of the 2,4 and 2,6 isomers. Each form of TDI was
reacted with hexanediol, other samples were pre- in some cases. Suggestions have been made that TDA
formation in polyurethane foams results from pH pared using a mixture of TDI, hexanediol, and a
small quantity of water (2% and 4% of hexanediol eects.10
To investigate this possibility a series of linear by weight).
The same TDI mixture was used to prepare a polyurethane samples of low molecular mass was
prepared by allowing TDI to react with a linear diol model commercial foam: a solution of dimethyl-
ethanolamine (03 g) in water (47 g) was prepared ( hexane-1,6-diol ). The advantage of a simple linear
Plastics, Rubber and Composites 2001 Vol. 30 No. 9
428 Hall et al. Toluenediamine in polyurethane foams
(i) in protocol 1, a toluene extract was prepared
by immersing a sample (1 g) of polyurethane
in toluene (10 mL) at room temperature for
24 h
(ii) in protocol 2, the polyurethane samples were
extracted with an aqueous acetic acid solution
(1% weight/volume), and the resulting solu-
tion then used directly for LCMS analysis or
extracted with dichloromethane (DCM) prior
to GCMS analysis
(iii) in protocol 3, the polyurethane samples were
extracted with aqueous acetic acid as in pro-
tocol 2, but sodium hydroxide solution was
0 200 400 600 800 1000 1200
0
Concentration/ppb
10
P
e
a
k

A
r
e
a
/
1
0
6
8
6
4
2
then added to pH 10 prior to DCM extraction
3 Calibration graph for mass spectrometric peak
and GCMS analysis; this protocol reects
area against concentration of TDA
those used in published work and these con-
ditions obviously favour hydrolysis of any poly-
urethane particles suspended in the aqueous
and mixed with polyol (Dow Voranol 3008, 928 g)
extractant.
using an electric mixer. A suspension of stannous
octanoate (18 g) in polyol (Dow Voranol 3008, 72 g)
was added followed by TDI (80:20 mixture of 2,4/2,6
RESULTS
isomers, 596 g). The reaction mixture was left to react
The results of the GCMS analyses of the various
overnight. The Dow Voranol 3008 has an average
extracts are presented in the form of total ion
molar mass of ~3000 g mol1 and a functionality of 3.
chromatograms (TIC) and mass chromatograms; the
A simple diurethane model compound was pre-
latter are for ions that are diagnostic of TDA. Where
pared by mixing phenylisocyanate (280 mg) with
appropriate, mass spectra are included together with
hexane-1,6-diol (140 mg) at ambient temperature, then
spectra from the Wiley and N.I.S.T. databases for
warming to 50C at which point the reaction mixture
comparison. A series of standard solutions of TDA
set to a solid mass. Sucient toluene was added to
was introduced into the GCMS instrument to identify
give a complete solution at reux. On cooling, crystals
the experimental parameters for the compound. The
formed and were collected by vacuum ltration.
TIC and corresponding mass spectra are shown in The various polyurethane samples thus prepared
Fig. 2. Figure 3 shows the correlation graph obtained. were characterised using gel permeation chromato-
The TIC (Fig. 4) generated by GCMS analyses of graphy and dierential scanning calorimetry. Solvent
toluene extracts obtained by protocol 1 showed a extraction was followed by GCMS or coupled liquid
peak at a retention time R
t
of 688 min; this was chromatographymass spectrometry (LCMS), which
assigned to hexanediol by comparison of the mass were used to determine the presence of TDA. The
spectrum with data from the Wiley and N.I.S.T. standard operating parameters for the instrumental
spectral databases (Fig. 5). No peaks were observed analyses are summarised in the Appendix. Three
that corresponded to either the retention time extraction protocols were used to assess the eect of
the experimental conditions, in particular pH: (~105 min) or mass spectrum of TDA.
tda pu 2,4/2,6 0% in toluene
6.00 8.00 10.00 12.00 14.00 16.00 18.00
Time 0
100
%
PU4TO Scan EI+
40_140
1.45e7
6.85
6.26
6.74
7.60
7.18
4 Mass chromatogram (GCMS) of toluene extract by protocol 1 (40140 Da)
Plastics, Rubber and Composites 2001 Vol. 30 No. 9
Hall et al. Toluenediamine in polyurethane foams 429
5 MS of peak at R
t
=688min in Fig. 4 identified as hexanediol by comparison with library data
Extracts obtained by protocol 2 were analysed by protocol 3 using GCMS as shown in Fig. 7. The
spectrum associated with the peak for TDA is shown high performance (HP) LCMS (details of the experi-
mental protocol are given in the Appendix). No in Fig. 8, along with the result of the library search.
The TIC obtained from the application of protocol 3 detectable amounts of TDA could be found as shown
by the mass chromatogram in Fig. 6. However, TDA to the diurethane model compound is shown in Fig. 9
with the corresponding mass spectrum in Fig. 10. was identied in the extract obtained by use of
1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00
Time 0
100
%
h29664a Sm (Mn, 1x2) 1: TOF MS ES+
123
30.6
2.57
0.26
1.31
0.79
1.73
1.86
8.40
8.02
6.04
4.90 4.37 4.11
3.89
2.88
5.62
7.91
6.52
7.67 7.23
6.85
8.61
8.83
9.83
9.49
9.12
(a)
TDA 10PPM
1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00
Time 0
100
%
t26400 1: TOF MS ES+
123
4.67e3
3.71
4.11
(b)
6 LCMS mass chromatograms showing: a absence of TDA in extract from protocol 2; and b TDA
(2,4 and 2,6 mixed isomers) standard (10 ppm) using same conditions as a
Plastics, Rubber and Composites 2001 Vol. 30 No. 9
430 Hall et al. Toluenediamine in polyurethane foams
tda pu 2,4, 2%
6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00
Time 0
100
%
Pu2dcm Scan EI+
122+121
1.23e5
10.66
11.15
7 GCMS chromatogram (121+122 Da) following protocol 3 extractions showing peak at R
t
=1066min
DISCUSSION are considered. Signicant amounts of TDA are found.
In this extraction procedure, the conditions are much
Linear polyurethanes
more favourable for hydrolysis of the urethane links,
yet this protocol diers essentially by the inclusion of Samples obtained by protocol 1
There was no evidence of TDA in the toluene extract. a basication step. Hydrolysis of polyurethane and
generation of TDA must therefore occur at this stage Hydrolysis reactions involving the urethane functional
group are not so favourable, since there are neither in the process.
aqueous nor basic conditions during the analysis
procedure.
Foam samples
Samples obtained by protocol 2
Samples obtained by protocol 1
There was no evidence of TDA in the aqueous acetic
The same reasoning can be used to explain the
acid extract. The fact that aqueous conditions were
GCMS results of foam extracts. In this case, a very
used in this extraction procedure does not seem to
small amount of TDI is found ( just at the limit for
cause hydrolysis of the urethane link as no TDA
detection) in the toluene extract. This could be due
was found. Furthermore, it would be expected that if
to either the thermal decomposition of urethane oligo-
any residual TDI were present in the polyurethane
mers in the injection port of the chromatograph or
samples before extraction, it would hydrolyse to form
unreacted TDI being present and extracted. No TDA
TDA under the aqueous conditions. The fact that no
was found however.
TDA can be found in these samples suggests that
Samples obtained by protocol 2
there is neither hydrolysis of TDI nor PU.
Neither TDI nor TDA were observed in these samples.
Any TDI would be expected to have hydrolysed under Samples obtained via protocol 3
Conrmation of the hydrolytic formation hypothesis the conditions of extraction, hence the TDI observed
from protocol 1 must arise from thermal degradation is obtained when the results of the analyses of non-
annealed polyurethane extracts obtained via protocol 3 of soluble oligomers.
8 Mass spectrum and library match corresponding to peak at R
t
=1066min from Fig. 7
Plastics, Rubber and Composites 2001 Vol. 30 No. 9
Hall et al. Toluenediamine in polyurethane foams 431
4.00 6.00 8.00 10.00 12.00 14.00 16.00
Time 0
100
%
TUBE1B Scan EI+
93+82
1.25e6
5.95
9.43
Extract in DCM Injector 250C
4.00 6.00 8.00 10.00 12.00 14.00 16.00
Time 0
100
%
TUBE1B Scan EI+
93+82
1.25e6
5.95
9.43
(a)
(b)
9 a GCMS chromatogram showing presence of hydrolysis products following treament of diurethane
model with alkali; b mass spectrum and library match of peak at R
t
=595min in Fig. 9a confirming
formation of aniline in diurethane hydrolysis experiment
Samples obtained by protocol 3 Diurethane model compound
Even a simple diurethane compound prepared from The amount of TDA found using protocol 3 is
~100 higher than the amount of TDI found by phenylisocyanate and hexanediol produced hydrolytic
degradation products (phenylamine, hexanediol, and protocol 1, suggesting that extensive hydrolysis of
the polyurethane has occurred during the extraction the corresponding monourethane) when treated with
aqueous alkali as in protocol 3. The formation and process, resulting in the formation of TDA.
2,4 tda std, pH 4
8.00 9.00 10.00 11.00 12.00 13.00 14.00 15.00 16.00 17.00 18.00
Time 0
100
%
TDA24_4 Scan EI+
TIC
2.57e5
14.24
10 GCMS total ion chromatogram of TDA extracted from aqueous solution at pH 4
Plastics, Rubber and Composites 2001 Vol. 30 No. 9
432 Hall et al. Toluenediamine in polyurethane foams
Luu et al.9 carried out a study in which the long
term hydrolysis behaviour of a poly(esterurethane)
foam was examined. The extraction was performed in
a phosphate buer (pH 74) at 37C for periods vary-
ing from 3 to 36 days and at 50C for periods varying
from 3 to 38 days. Additionally, an extraction in
DCM was performed at 37C for 60 days. The extracts
were decanted at the appropriate times and worked
up using a method that employed alkaline and acidic
conditions. Both HPLCUV and GCMS analyses
were then undertaken. The poly(esterurethane) foam
+
C N O
N
H
C
O
O
O
C N
H
O
O
O
H
H
was found to produce 2,4 and 2,6-TDA (detection
11 Formation and hydrolysis of diurethane model
limit 1 ppb) continuously in the phosphate buer extract
compound
over 36 days of extraction at 37C, and at 50C,
greater amounts of TDA (up to 25) were found. In
the DCM extract, minimal amounts of TDA were hydrolysis of the model compound is shown in Fig. 11.
found. They conclude that under the mild aqueous After extraction via protocol 3 and GCMS analysis,
conditions at 37C and 50C, polyurethane foam is various compounds were found as shown in Fig. 12.
susceptible to hydrolytic degradation, producing TDA. These products are clearly hydrolytic degradation
products of the model compound, and these ndings
show that by using protocol 3, the risk of hydrolysis
CONCLUSIONS of urethane functions occurring is high.
Based on these observations and the ndings of Luu
et al.9 and Amin et al.,10 it is suggested that the
Comparison with literature reports
reported observations of TDA in polyurethane foam
In general, the results of the GCMS and LCMS
by Skarping et al. quoted in the Swedish and Danish
analyses are in good correspondence with the ndings
press11 are due to the highly alkaline conditions that
of Amin et al.,10 who used a coupled system of high
were used during extraction. Skarping et al.,4 describe
performance liquid chromatography (HPLC) and UV
the use of a saturated solution of sodium hydroxide
spectroscopy to analyse a poly(esterurethane) foam
(~15 mol dm3). This strongly alkaline solution
under a variety of physiological and non-physiological
increases the possibility of hydrolysis especially if this
extraction and hydrolytic conditions. At the detection
solution comes into contact with oligomeric urethanes
limit of 20 ppb, no TDA could be detected in aqueous
or polyurethane particles in the extract.
buer extracts or in a phosphate buer extract, but
Whereas strongly alkaline solutions need to be
with slightly alkaline conditions (pH 74) small oligo-
used to hydrolyse protein conjugates in biouids and
mers were detected. However, when the foam came
thereby release bound amines, such conditions should
in contact with even a low concentration of strong
be avoided when there is any possibility of urethane
mineral acid or base, high levels of TDA were found.
compounds being present and are therefore inappro-
Whereas 5 days of incubation in aqueous buers or
priate for the analysis of polyurethane foam extracts.
phosphate buers did not lead to the formation of
With a pKa of the order of 35 it is not necessary to
TDA, 15 min exposure to 01 M HCl or 1 M KOH
raise the pH above neutrality in order to extract TDA
resulted in signicant amounts of TDA being formed.
from an aqueous solution. The total ion chromato-
They therefore suggest that TDA formation in poly-
gram from a dichloromethane extract of an aqueous
urethane foams results from pH eects on oligomeric
solution of TDA at pH 4 is shown in Fig. 10.
polyurethane fragments in or extracted from the
In answer to the question TDA in polyurethane
foam. They also cite extremes of heat or pH during
foams hazard or artefact?, it can be concluded that
preparation of PU foam extracts as likely causes of
if an inappropriate extraction protocol is used, then
the formation of TDA.
TDA could be formed during the analysis and hence
is an artefact.
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Hall et al. Toluenediamine in polyurethane foams 433
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APPENDIX
programme was 45C for 1 min, then 6 K min 1
GCMS parameters
heating rate up to 225C. The carrier gas used was
Fisons Instruments MD800 system tted with electron helium at 60 kPa and the injection was 10 mL at
250C. impact source operating at 70 eV in positive ion mode.
Plastics, Rubber and Composites 2001 Vol. 30 No. 9