Polymer Degradation and Stability 50 (1995) 313-317
0 1995 Elsevier Science Limited
Printed in Northern Ireland. All rights reserved
0141-3910/95/$09.50
ELSEVIER 0141-3910(95)00156-5
Antioxidant-induced yellowing of textiles
0. D. Bangee: V. H. Wilson: G. C. East6 & I. Holme’
“British Textile Technology Group, Didsbury, Manchester M20 2RB, UK
hLeeds University, Department of Textile Industries, Leeds LS2 9JT, UK
(Received 14 May 1994; accepted 13 July 1995)
The yellowing of white and pastel coloured textiles and garments has been a
problem for many years in the textile industry. In the last 15 years much
evidence has been published which suggests that a large proportion of storage
yellowing is attributable not to the yellowing of fibre substrate or textile finish
but to the yellowing of phenolic antioxidants which migrate onto the textiles
from polyethylene and polypropylene packaging. These mobile phenolic
compounds interact with atmospheric pollutants, particularly oxides of nit-
rogen, to give yellow compounds. A brief outline of the problems of yellowing
is given, together with the identification of the yellow substances produced by
BHT (2,6-di-tert-butyl-4-methyl phenol) and possible mechanisms of their
formation. ProDhvlactic measures that can be taken bv the earment manufac-
I I
turer and finisher to prevent or minimise yellowing a& also Discussed
1 INTRODUCTION ute) and other laboratories, it is now well known
that the most frequent cause of yellowing arises
Yellowing of white and pastel coloured textiles from the interaction of oxides of nitrogen with
and garments has been a problem for many years phenolic antioxidants.
in the textile industry. The phenomenon of
yellowing can arise from many separate causes,’ 1.1 Oxides of nitrogen (NO,)
for example, microbial attack,2 yellowing of
fluorescent brightening agents,3’4 dyestuff migra- Waste gases, particularly oxides of nitrogen, are
tion from cardboard packaging,’ photochemical now widely recognised as an important part of
and thermal influence on fibres, etc. However, the yellowing problem.6-8 These gases are present
the greatest number of complaints have been in air pollution and in many areas their levels
received from manufacturers who do not observe have increased in spite of pollution control. Nitric
the yellowing until the fabric has actually been oxide (NO) and nitrogen dioxide (NO,) are
made up into garments and stored in pol- formed in combustion processes. Nationally,
yethylene or polypropylene bags in warehouses motor vehicles account for approximately half of
and stockrooms. the total emissions of NOx, with power stations
The discovery of the yellowed goods so late in and industry accounting for a further 35% of
the complex textile production chain leads to emissions. Almost all oxidised nitrogen pollution
considerable difficulties in determining liability is emitted as nitric oxide, which at ambient
for the financial loss. Losses of f20 000-30 000 or temperatures tends to oxidize to the more toxic
more can result from a single case of yellowing. secondary pollutant nitrogen dioxide. This
The actual cause of yellowing depends upon process is accelerated in the presence of sunlight,
different factors such as materials used for reactive hydrocarbons and ozone.
packaging, storage conditions, atmospheric
pollution, processing conditions and textile 1.2 Phenolic antioxidants
auxiliaries.
After many years of research into this growing The widespread use of polyethylene and
problem of yellowing by the British Textile polypropylene bags for storage of all manner of
Technology Group (formerly the Shirley Instit- textile materials is another major factor that can
313
314 0. D. Bangee et al.
provoke yellowing.9~10 The reason is that most or is much decreased when exposed to
polyethylene and polypropylene bags contain sunlight for a few days or more.
antioxidants, which extend and/or maintain the 4. Effect of change in pH: reversible
polymer’s useful service life by inhibiting or acid/alkali effect. Generally alkalis (e.g.
retarding oxidation. NH, vapour) intensify the coloration, while
One of the most common antioxidants, acid vapours lighten or remove it.
encountered in numerous cases of yellowing, is 5. Extraction of yellow stain: the yellow
2,6-di-tert-butyl-4-methyl-phenol (BHT). It is substance is largely extracted by organic
used for the stabilization of packaging films, solvents, e.g. methanol. Spectra of the
because it is cost effective and is approved by the extracts give absorption peaks at 420 or 450
US Food and Drug Administration and other nm, or both wavelengths. After addition of
national regulatory agencies.“,12 However, its one alkali, the peak at 450 nm becomes much
major drawback is its high volatility. With time it more prominent, that at 420 nm being less
migrates to the surface of the film and is then lost in evidence.
to the atmosphere. As much as 1% by weight of 6. pH level of fabric: the pH level of the fabric
BHT may be lost each day at normal is normally 5 or higher in stained areas of
temperatures.13 fabric.
2.2 Analysis of oxidation/nitration products
2 EXPERIMENTAL from BHT
An investigation was carried out on a polyester- The yellowed area from the shirt fabric was
cotton shirt submitted to the laboratories of extracted with HPLC grade methanol and then
BTI’G. The shirt was wrapped in a BHT subjected to thin layer chromatography. The
stabilized polyethylene bag, which was slightly separated spots were then analysed by suitable
open at one end. The shirt was stored at the techniques such as infrared and UV/VIS
manufacturer’s warehouse, which was heated by spectroscopy and high performance liquid chro-
an open gas fire. matography. Identification was performed by
Examination of the fabric showed that comparison with spectra obtained from the
yellowing had occurred especially near the literature, and with spectra of authentic com-
opening in the bag. pounds prepared in the laboratory.
2.3 Preparations of compounds (I)-(VIII)
2.1 Preliminary tests
Compounds (I)-(VIII) (see Scheme 1) were
At the onset of investigation of any individual
synthesised according to conventional methods,‘“‘8
yellowing case, it is useful to conduct some and purified by recrystallization.
preliminary tests to indicate whether phenolic or
some other type of yellowing is involved. The
main tests usually undertaken are listed below, 3 RESULTS AND DISCUSSION
together with the results normally associated with
phenolic yellowing. It is now clear what happens in actual cases of
1. Colour: the stain is lemon yellow. yellowing of fabrics. The fabric, which is finished
2. Spot test for nitrite:4 detects the presence of slightly on the alkaline, side is processed into the
nitrogen dioxide absorbed by the fabric garment, e.g. blouse, shirt, bedsheet, etc., and
using Saltzman’s reagent (a mixture of then placed in a polyethylene or polypropylene
acidified sulphanilimide and N-1-naphthyl bag containing BHT (or another sterically
ethylenediamine dihydrochloride). The nit- hindered phenolic antioxidant). The bagged
rogen dioxide diazotizes the amine, which garment is then stored in a warehouse in which
then couples with the sulphanilimide, giving air contaminated with oxides of nitrogen is
a pink-red colour, the intensity of which circulating. This period of storage can vary from
indicates the amount of nitrogen dioxide. 1 or 2 weeks to a few months, during which the
3. Exposure to sunlight: the stain disappears BHT migrates from the bag and interacts with
Antioxidant-induced yellowing of textiles 315
oxides of nitrogen to form yellow stains on A number of other, slightly coloured or
certain parts of the garment. colourless products were also identified. Prop-
After extraction of the yellowed area from the osed mechanisms for the chemical reactions that
fabric and subsequent analysis by IR, UV/VIS take place are given in Scheme 1.
and HPLC, three yellow compounds were It is generally accepted that the formation of a
identified, and are discussed below. phenoxy radical by homolytic oxidation of the
phenol by nitrogen dioxide or oxygen is a likely
mechanism of initiation. Delocalisation of the
3.1 3,3’,5,5’-Tetra-tert-butyl-4,4’-stilbenequinone
unpaired electron in the phenoxy radical yields
(SQ)
three mesomeric structures in equilibrium.
Isomerization to a benzyl radica11”.21-2’followed
The stilbenequinone is derived from BHT by
by dimerization yields the colourless dibenzylqu-
oxidation, and many oxidants, including nitrogen
inol (BHPEA, V) and the highly coloured
oxides, oxygen and polymer peroxy compounds,
stilbenequinone (SQ, VI). It has been suggested
can cause this transformation. The solid state
by Smeltz2” that SQ can also be formed via
compound is brick red in colour and gives a very
nitration at the para position by NO, to give a
intense yellow solution. In polar solvents it has a
quinonitrole (MQN, IV), which is unstable and
maximum absorption at 444 nm. It has been
slowly decomposes to a substituted quinone
estimatedIg that only 0.8 ppm of SQ produces a
methide (QM). This subsequently dimerizes to
visible yellowing of fluorescent white goods.
BHPEA and SQ. However, Wilson” believes
that MQN hydrolyses to form a stable quinol
3.2 3,3’,5,5’-Tetra-tert-butyl-4,4’- (MQOL, VIII) and that the SQ is not formed
diphenoquinone (DPQ) directly from MQN.
The mechanism for the formation of the
This compound is also brick red in colour in the pH-sensitive nitrophenol is still unclear. It is
solid state and gives an intense yellow colour in likely that it is formed via the benzyl alcohol
methanol, with an absorption maximum at 419 (BALC, I) and the benzaldehyde (BALD, II),
nm and a shoulder at around 400 nm. It has a which are formed in small quantities via
melting point of 231°C. oxidation of BHT. Experiments in which cotton
fabric impregnated with the benzyl alcohol and
3.3 2,6-Di-tert-butyl-4_nitrophenol(NP) the benzaldehyde is exposed to 5-10 ppm NO,
showed that both these compounds readily
The nitrophenol has a melting point of 157°C and convert to the nitrophenol. It is possible that the
in non-polar solvents is colourless to pale yellow diphenoquinone (DPQ, VII) forms via the
and shows two absorption maxima (320 and 420 nitrophenol.
nm), the latter about half as intense as the
former. On addition of 2% NH, to the methanol
solution the maximum at 320 nm disappears and 4 PREVENTION OF YELLOWING
there remains only the maximum at 450 nm with
a strong increase in intensity of yellow. The
intensity of the yellow colour depends on NO, has been identified as one of the major
whether the nitrophenol is in the benzenoid (A) causative agents for yellowing of textiles. So it is
or quininoid (B) form.” important to ensure that the gas- or oil-fired
heating systems employed in mills do not
OH 0 give rise to high nitrogen dioxide emissions
and also that emissions from motor vehicles
are not allowed to accumulate in the storage
area.
The yellowing could be prevented by selecting
high quality packaging that does not contain
volatile antioxidants like BHT. Some high
(A) m molecular weight antioxidants, for example
Colourless Yellow Irganox 3114 and Cyanox 1790, are not very
316 0. D. Bangee et al.
OH
N*z
-
BALD (II)
OH 0
N4
-
f CH,OH
BALC (I)
OH
1; -
*
CH3
BHT
MQ*L VW MQN (rv) QM
Scheme 1. Proposed mechanism for BHT yellowing.
volatile and are fairly resistant to yellowing by REFERENCES
NOz.
The selection of good quality textile auxiliaries,
which are free from phenolic derivatives, 1. Hemmpel, W. H., Text. Praxis ht., 38 (1983) 261.
2. Mebes, B., Conf. Yellowing of Textiles, p. 49. Waregem,
especially for fabric finishing, is essential. 1983.
Another way to prevent yellowing is to finish 3. Martini, T., Text. Progr., 15 (1987) 16.
the white fabrics on the acid side, with use of low 4. McEwan, J., & Murdoch, W., J. Sot. Dyers Colourists,
97 (1981) 279.
volatility chemicals such as citric acid. It is 5. Niemann, I., Text. Praxis Znt., 35 (1980) 1041.
generally suggested that if white fabrics are 6. Salvin, V. S., Book of Papers, p. 40. AATCC Nat1 Tech.
acidified to pH 5 or less, the yellowing problem Conf., 1974.
could be decreased. 7. Ward, C. D., Knitting Ind. Tech. Rev., 1 (1981) 60.
8. Ward, C. D., Text. Progr., 15 (1987) 7.
9. Ciba Geigy, Tech. Bull. TCB4/79, May (1979).
10. Hemmpel, W. H., Text. Praxis Znt., 35 (1980) 1213.
11. Code of Federal Regulations, Title 21, Part 182.
ACKNOWLEDGEMENT Government Printing Office, Washington, DC.
12. Code of Federal Regulations, Title 9, Part 318.7~.
Government Printing Office, Washington DC.
This project was funded by the Department of 13. Wilson, V. H., Text. Inst. World Conf., Dundee, 1990.
Trade and Industry and the Engineering and 14. Coppinger, G. M., & Campbell, T. W., J. Am. Chem.
Physical Sciences Research Council under the Sot., 75 (1953) 734.
1.5. Barnes, T. J., & Hickinbottom, W. J., J. Chem. Sot.
Postgraduate Training Partnership Scheme. (1961) 953.
Antioxidant-induced yellowing of texr‘les 317
16. Kharasch, M. S. & Joshi, B. S., J. Org. Chem., 22 (1957) 20. Wagner, H., Text. Praxis ht., 17 (1984) 355.
1439. 21. Cosgrove, S. L. & Waters, W. A., .I. Chem. Sot. (1951)
17. Bohn, C. R. & Campbell, T. W., J. Org. Chem., 22 388.
(1957) 458. 22. Bennet, J. E., Nature (1960) 385.
18. Cook, C. D., Nash, N. G., & Flanagan, H. R., J. Am. 23. Wilson, V. H., PhD thesis, University of Salford, 1990.
Chem. Sot., 77 (1955) 1783. 24. Smeltz, K. C., Textile Chemist and Colorist, 15 (1983)
19. Schmidt, E., Textilueredlung, 17 (1982) 254. 52.