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Migration from polyethylene

terephthalate under all conditions
of use
a
R. Ashby
a
ICI Wilton Materials Research Centre , PO Box No 90,
Wilton Middlesbrough, Cleveland, TS6 8JE, UK
Published online: 10 Jan 2009.

To cite this article: R. Ashby (1988) Migration from polyethylene terephthalate

under all conditions of use, Food Additives & Contaminants, 5:S1, 485-492, DOI:
10.1080/02652038809373681

To link to this article: http://dx.doi.org/10.1080/02652038809373681

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 FOOD ADDITIVES AND CONTAMINANTS, 1988, VOL. 5, SUPPLEMENT NO. 1, 4 8 5 - 4 9 2

Migration from polyethylene terephthalate under all conditions of use

R. ASHBY
ICI Wilton Materials Research Centre, PO Box No 90, Wilton Middlesbrough, Cleveland
TS6 8JE, UK

The condition of time and temperature under which PET (polyethylene terephthalate) is
used in food contact applications is reviewed. The effect upon overall migration into fat
simulants of varying temperature, time, thickness and crystallinity of the PET is discussed,
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with experimental data. Specific migration of monomers, catalyst residues, colourants and
acetaldehyde from PET into food simulants is reported.

Keywords: Food contact materials; Polyethylene terephthalate; Global and specific

migration

Polyethylene phthalate (PET) polymers have been used in contact with food for
many years. In its initial fibre form its use was restricted to dry foods or in filters.
Now that it is available in film, foil and bottle form its uses have increased
considerably. As a biaxially oriented film it has strength, flexibility and clarity, and
can be used alone as roaster bags for oven cooking. PET film has been most widely
used as a component of laminates to give mechanical strength and barrier
properties, particularly when metallized. Typical applications have been in vacuum
packs and modified or controlled atmosphere packs. The good resistance to high
temperature has allowed PET-based laminates to be used in boil-in-the-bag and
retortable pouches. In most of these applications the PET has not been in direct
contact with the food, owing to the difficulty of sealing PET bags. However,
co-extruded copolymers of polyethylene terephthalate with isophthalates, for
example, do give acceptable seals, and these are now used in applications such as lids
for PET containers.
The major increase in the use of PET in direct contact with food came with
bottles. PET bottles are now extensively used for carbonated soft drinks, mineral
waters, beers, wines, spirits and edible oils. In the future PET bottles and containers
are likely to find even wider applications.
Another major increase in the use of PET for direct contact is as trays for use in
conventional and microwave ovens. Frequently food is stored in the trays in the
freezer and then reheated in the tray before serving. Even complete meals are
available packaged in this way. With the increased use of microwave ovens has come
the need for trays for repeated use; these are now being made by injection moulding
PET.
The conditions under which PET is used are now extremely varied. The food
types in contact with PET include even the most aggressive extractants such as
spirits, with an alcoholic content of 40% or more, and edible oils. Similarly, the
times and temperatures experienced by PET in contact with food can be very
aggressive. These include the extremes of prolonged contact, i.e. 6 month or more,
at room temperature or below, and up to 2 hours contact at oven cooking
temperatures exceeding 200° C.
 486 R. Ashby

All of these possible conditions of use must be considered when assessing the
possible migration of components from PET into food. Fortunately the
formulations of PET for food contact use are relatively simple, since the extensive
use of plasticizers, antioxidants or stabilizers is not required. However, colourants,
both dyes and pigments, and additives such as fillers and nucleating agents, are
commonly added to PET. From the polymer itself residual monomers, such as
ethylene glycol or terephthalic and isophthalic acid, oligomers and degradation
products, such as acetaldehyde, and catalyst residues may migrate.
Many factors may play a part of influencing the potential for migration from
PET to foodstuffs. The most obvious is the nature of the foodstuff itself, that is its
fat or alcohol content and acidity, and the time and temperature of exposure. Other
factors depend on the polymer characteristics—for example, orientation and
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molecular weight or on the geometry of the package, e.g. thickness and surface to
volume ratio.
A number of experiments have been conducted and observations made at the
ICI Research and Technology Department at Wilton to assess the effect of these
various parameters on the overall migration from PET.
The first effect to be considered was food type. Table 1 shows the overall
migration from PET 2-litre bottles that occurs during exposure at 40° C for 10 days
to the following food simulants, water, 3% w/v aqueous acetic acid, 15% v/v
aqueous ethanol, 50% v/v aqueous ethanol and olive oil. Overall migration into the
aqueous simulants is less than that into the olive oil. Similar trends have been
observed with film and foil samples. Indeed, throughout the many determinations
of overall migration into aqueous simulants carried out by ICI, even including
exposure at reflux temperatures for 2 hours, no overall migration exceeding the
2 mg/dm2 level was observed. The scatter of results in the olive oil migration
experiments with negative results is typical of PET samples. This scatter, and

Table 1. Overall migration into different types of

food simulants
Temperature 40 C
Time 10 days
Sample thickness 350 ^m
Surface area 2 dm2
Volume of simulant 100 ml
Type of exposure total immersion
Sample type PET bottle wall

Overall
migration
Food simulant (mg/dm2) Mean

Water 0-35 0-33

0-30
3% aqueous acetic acid 0-52 0-53
0-53
15% aqueous ethanol 0-38 0-38
0-37
50% aqueous ethanol 0-59 0-57
0-55
Olive oil -1-1 0.7
+ 0-9
+ 2-3
 Migration from polyethylene terephthalate 487

negative values, may well be caused by the difficulty in reaching constant weight at
50% relative humidity before and after exposure to the olive oil.
The next parameter to be considered was temperature. Samples from a biaxially
oriented PET film of thickness 125 fim were exposed to olive oil for 10 days at the
following temperatures; 5,40,70,121 and 175°C. The results are given in table 2.
There is not a progressive increase in migration with temperature. This is unlike the
nearly linear relationship between the logarithm of overall migration and the inverse
of absolute temperature which we reported for low-density polyethylene at the
Fourth International Migration Symposium. However, the migration results at
175°C, well above the glass transition temperature range of about 80-110°C, are
consistently positive.
After temperature the next parameter to be considered was time. Once again,
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samples from a biaxially oriented film, 125 ^m thick, were exposed at 175°C for the
following times, 2, 24 and 240 hours (10 days). The results are given in table 3 and
shown graphically in figure 1. From the graph, where overall migration is plotted
versus the square root of time, it can be seen that at this high temperature of 175°C
classical thermodynamics are obeyed and there is a linear relationship.
The next parameter investigated was thickness, and biaxially oriented films of
thickness, 23, 50 and 125 microns were exposed to olive oil at 175°C for 24 hours.
The results are given in table 4 and shown graphically in figure 2. Once again the
results are as might be expected with a not quite linear relationship, the migration
from thick samples being reduced as the olive oil fails to penetrate the thicker
sample.
The effect of varying surface to volume ratio was also investigated by exposing
a biaxially oriented 125 /*m PET film to 110 cm3 of olive oil at 40°C for 10 days with

Table 2. Variation of overall migration into olive oil

with temperature

Time 10 days
Sample thickness 125 pm
Surface area 2 dm2
Volume of oil 100 ml
Type of exposure total immersiori
Sample type PET biaxially oriented film

Overall
Temperature migration
(°Q (mg/dm2) Mean

5 -0-9 -0-4
+ 0-1
40 -0-8 -0-3
+ 1-1
-1-2
70 -0-8 -0-4
-0-4
-0-1
121 -2-7 -2-4
-0-1
-4-5
175 36-3 + 34-8
32-7
35-3
 488 R. Ashby

the following areas 1, 2 and 4 dm2. These results, shown in table 5, indicate that
within experimental error there is no detectable difference in migration level with
changes of surface area in contact with the same volume of oil at 40°C.
Finally, the effect of orientation has been investigated. PET polymers of similar
molecular weight (IV of about 0*73) were used to produce a bottle and a cast foil,
both with a thickness of 350 /*m. The results of overall migration testing at 40°C are

Table 3. Variation of overall migration into olive oil

with time

Temperature 175 C
Sample thickness 125 fim
Surface area 2 dm 2
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Volume of simulant 100 ml

Type of exposure total immersion
Sample type PET biaxially oriented film

Overall
Time migration
(hours) (mg/dm 2 ) Mean

2 3-8 4-0
3-8
4-4
24 4-5 6-9
7-6
8-6
240 36-3 34-8
32-7
35-3
 Migration from polyethylene terephthalate 489

shown in table 6, which shows a significantly higher level of migration from the
amorphous cast PET compared to the blown bottle. The bottle was blown with a
draw ratio of about 2-5 but was not heat-set. The difference between the samples
was therefore the orientation of the PET molecules in the bottle.
In addition to determining overall migration from PET, the migration of
specific components of the PET was also investigated.

Table 4. Variation of overall migration into olive oil

with thickness

Temperature 175 C
Time 24 h
Surface area 2 dm 2
Volume of simulant 100 ml
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Type of exposure total immersion

Sample type PET biaxially oriented film

Overall
Thickness migration
(lim) (mg/dm 2 ) Mean

23 1-9 2-0
1-9
2-1
50 4-5 5-0
5-7
4-8
125 4-5 6-9
7-6
8-6

20 40 60 80 100 120
Thickness (/im)
Figure 2. Overall migration versus thickness
 490 R. Ashby

Pira have, as part of their recent Migration Project, determined the specific
migration of terephthalic acid and isophthalic acid from PET into foods and food
simulants. The results, given in table 7, show that the migration of these monomers
from film and bottle samples is extremely low.
Ethylene glycol and diethylene glycol, the possible by-product of PET
polymerization, have been analysed in aqueous ethanol extracts from PET film and
bottles after exposure for 10 days at 40°C. The results are given in table 8. In all
cases, neither ethylene glycol nor diethylene glycol was detected by a gas
chromatographic method with a detection limit of 15 ppm for both glycols.
The migration of catalyst residues has also been investigated, in particular

Table 5. Variation of overall migration into olive oil

with surface area per volume
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Temperature 40 C
Time 10 days
Volume of oil 100 ml
Type of exposure total immersion
Sample type PET biaxially oriented film

Surface area Overall

per volume migration
(dm/100 ml) (mg/dm 2 Mean

1 -0-5 + 0-2
-0-5
+ 1-7
2 -0-8 -0-3
+ 1-1
-1-2
4 + 0-1 -0-2
-0-1
-0-5

Table 6. Variation of overall migration into olive oil

with orientation
Both samples were of 350 fim thickness, made from
polymer of similar molecular weight

Temperature 40 C
Time 10 days
Surface area 2 dm 2
Volume of oil 100 ml
Type of exposure total immersion

Overall
migration
(mg/dm 2 ) Mean

Two-litre oriented bottle -1-1 0-7

+ 0-9
+ 2-3
Amorphous cast film 2-2 2-3
2-5
2-1
 Migration from polyethylene terephthalate 491

antimony and cobalt. The results are given in table 8 and show that these catalyst
residues have low levels of migration even at high temperature.
Another migrant arising from the polymer is acetaldehyde. The factors
affecting the migration of acetaldehyde are more complex, since it may be
manufactured during fabrication of the test sample and possibly also during
exposure to simulants at high temperature; also, being more volatile, it
spontaneously migrates. In our experiments the levels of acetaldehyde migrating
into water under reasonable storage conditions have peak values of less than 50 ppb.

Table 7. Migration of terephthalic acid and isophthalic acid

(mg/kg) after 10 days at 40°C (determined by Pira)
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Terephthalic Isophthalic
Simulant acid (mg/kg) acid (mg/kg)

Film (2 dm2 in 100 ml simulant)

Distilled water <0-01 <0-05
3% aqueous acetic acid <0-01 <0-05
15% aqueous ethanol <0-01 <0-05
Olive oil 0-03 <0-05

Bottle (50 ml)

50% aqueous ethanol 0-02 <0-05
Vodka 0-03 <0-05

Table 8. Specific migration results from PET bottles

Exposure
Food temperature Exposure
Migrant simulant <°C) Time Result

Acetaldehyde water 55 8 days peak values < 50 ppb

water 40 10 days peak values < 15 ppb
Ethylene glycol 15% ethanol 40 10 days nd < 15 ppm
55% ethanol 40 10 days
Diethylene glycol 15% ethanol 40 10 days nd < 15 ppm
55% ethanol 40 10 days

Catalyst residues
Antimony water
3% acetic acid 40 10 days nd < 10 ppb
15% ethanol
olive oil
HB3O7 230 2h nd < 10 ppb
Cobalt water
3% acetic acid 40 10 days nd < 3 ppb
15% ethanol
olive oil
HB307 230 2h nd < 3 ppb
Colourant water
(anthracene 3% acetic acid 49-5 21 days nd < 50 ppb
dyestuff) 50% ethanol
n-heptane
 492 Migration from polyethylene terephthalate

For many bottle applications PET is coloured, particularly with polymer-

soluble dyes. A typical dye used is an anthracene dye giving a yellow colour.
Migration studies with the food simulants show that after exposure at 49'5OC for 14
days migration of this colourant into the food simulants is not detectable at the 50
part per billion level.
In conclusion, the specific migration results show that the constituents of
PET—such as monomers, catalysts, residues and breakdown products—have very
low levels of migration into all types of food when tested under conditions
simulating realistic conditions of use, i.e. low temperatures or short-duration tests at
high temperatures.
The higher overall migration values are therefore presumably a measure of the
PET oligomers which are migrating. Above the glass transition temperature range of
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80-110°C, overall migration into olive oil can occur in measurable quantities.
Below 80°C the overall migration into olive oil is low except for amorphous PET.
The method currently being used to determine overall migration at temperatures of
120°C and below is not capable of measuring the low migration with precision.