| Structural Formula

Polyethylene Terephthalate
Migration and Toxicity
M = 20,000 to 40,000 CAS No 29154-49-2 Abbreviation. PET.
Synonyms and Trade Names. Amilar; Daiya foil; Dowlex; Ethylene
terephthalate polymer; Fiber V; Hostadur; Hostaphan; Lavsan; Lawsonite;
Melinex; Mersilene; Nitron lavsan; Poly(oxy-1,2-ethanediyloxycarbonyl-1,4phenylenecarbonyl);
Polyethylene glycol terephthalate; Terephtahlic acid-ethylene
glycol polyester.
Composition. A polyester of terephthalic acid and ethylene
glycol can be obtained by the poly= condensation of dimethyl terephthalate
(q.v.) with ethylene glycol, and also terephthalic acid with ethylene
glycol or ethylene oxide.
Properties. A white or light-cream material. Noted for
high heat resistance and chemical stability. When melt-blown,
it provides a good barrier for both flavors and hydrocarbons (fat).
It is not transparent. PET is resistant to acids, bases, some
solvents, and oils and fats. It is difficult to mold. The melting
point of unmodified PET is below boiling. Monolayer films will
hold a crease, are heat sealable, and transparent. Dens. 1.33220.
M. p. 255 to 265°C. n25 =1.574. Insoluble in water.
Applications. PET is used for high-impact resistant containers.
It is used for packaging of soda, mouthwash, pourable dressings,
edible oils, and peanut butter. It is used for cereal box liners,
soda bottles, boil-in-the-bag pouches, and microwave food trays.
Modified PETS can be heated in a microwave or in a conventional
oven at 180°C for 30 minutes. There has been a moderate amount
of concern that additives from these trays may migrate into foods,
particularly if the trays are reused in a microwave oven. PET
is also used in the production of different bottles, fibers, films
for food packaging, and different articles. Lavsan fabric is used
in the dairy industry for filtering. Used in medicine for plastic
vessels and for implantation.
Migration Data. A total of 19 migrants from commercial amber
PET bottle wall has been identified by GC/MS analysis: the majority
of compounds appeared to be intermediate reaction products or
residual monomers of their dehydration and transesterification
products. Fatty acids and commonly used plasticizers were also
identified.1
Quantities of PET cyclic oligomers found in the microwaveable
French fries, popcorn, fish sticks, waffles, and pizza ranged
from less than 0.012 to approximately 7.0 g/kg.2
PET contains detectable amounts of acetaldehyde, which is able
to migrate from the polymer into liquid media With the help of
a static headspace GC method, acetaldehyde was found in carbonate
mineral water and lemonade. Acetaldehyde concentration ranged
between 11 and 7.5 mg/l, while the contents of acetaldehyde in
the PET packages ranged from 1.1 to 3.8 µg/g.3
Migration of acetaldehyde from PET at 40°C reached
a constant level after 4 days which was about 10% of the residual
value of acetaldehyde (6.3 mg/kg). At 60°C this level was
raised up to 50%.
PET caused no changes in the taste of soft drinks containing carbonic
acid when exposed at lower temperature and over a relatively short
period of time 4 Lavsan material had no effect on the taste and
odor of aqueous extracts, nor on their oxidizability. Migration
of antimony ion (catalyst) into water was not observed.07 Piekacz
discovered migration of calcium and magnesium ions from pellets
and film. Diethylene glycol and dimethyl terephthalate were not
found in extracts.5
PET samples including laminates, bottles, and roasting bags, were
heated at 120, 150, and 230°C for 50 min, according to sample
type. Volatiles released from the material were identified by
GC-MS and assessed against a 10 mg/kg migration threshold limit.
The main substances identified were not related to PET, but probably
came from printing inks and adhesives. Authors concluded that
the migration potential of PET in high temperature applications
is very low and that the formation of volatiles during use is
unlikely to cause any special problems in polymer recovery in
recycling schemes.6
Migration of ethylene glycol (EG) from PET bottles stored
at 32°C for 6 months into the food simulant 3.0% acetic acid
was studied by gas-liquid chromatographic procedure and observed
at the level of about 94 µg EG/bottle.7
Migration of residual contaminants remaining in the extruded
PET (benzene, butyric acid, dodecane, octadecane, tetracosane,
diazinon, lindane, and cooper ethyl hexonate) into food-simulating
solvents, aqueous ethanol, and heptane, resulted in concentrations
lower than 0.01 mg/kg. Authors concluded that unwashed recycled
PET may not comply with FDA requirements.
Migration of antimony from PET into food simulants, measured by
inductively-coupled plasma-mass spectrometry amounted to 4.0 µg/kg.
The concentration found was less than proposed limit of migration.9
Migration from colored PET bottles for carbonated beverages
was studied. PET bottles filled with naturally carbonated mineral
water up to 6-month storage released total organic carbon within
the EEC and FDA limits. The following migrating substances were
identified by GC-MS analysis: acetaldehyde, dimethyl terephthalate,
and terephthalic acid. 10
Acute Toxicity. Neither administration of PET powder nor
a single administration of chloroform extracts of PET at a dose
of 10 g/kg BW had a toxic effect on rats."
Repeated Exposure. In a 1-month study, rats received wine
extracts obtained after several months contact withPET. The treatment
produced no harmful effect on animals. 12
Short-term Toxicity. Rats were given 5.0 to 400 mg technical
grade PET/kg BW and 5.0 to 100 mg pure PET/kg BW over a 3-month
period. There were no changes in their behavior, BW gain, biochemical
indices of blood serum, urine, or hematology analyses, or in relative
weights of internal organs."
Long-term Toxicity. No manifestations of toxicity were observed
in rats, given aqueous extracts of PVC film reinforced with Lavsan.
13
Mutagenicity.
In vitro genotoxicity. De Fusco et al. studied the mutagenicity
in unconcentrated mineral water stored in PET bottles and growing
Salmonella strains directly in the plastic bottles. Leaching of
mutagens after 1 month of water storage in daylight and in the
dark in PET bottles used for beverage packaging was noted. This
activity washigher after storage in daylight. 14 The mutagenicity
test on non-volatile migrant compounds identified in the above-sited
study gave negative results. 10
Carcinogenicity. Dacron induced malignant tumors at the
site of application in rodents following s/c imbedding of polymer
films. Nevertheless, the results of this study have been later
considered inadequate. 026 S/c implantation of pieces of PET graft
to mice and Syrian golden hamsters showed no statistical evidence
of tumor induction. Observation period was 73 and 82 weeks, respectively.
15
Regulations. U.S. FDA (1998) approved the use of PET as
components of polyethylene phthalate polymers intended for use
in contact with food in accordance with the conditions prescribed
in 21 CFR part 177.1630.
References:
1. Kim, H., Gilbert, S. G., and Johnson, J. B.,
Determination of potential migrants from commercial amber polyethylene
terephthalate bottle wall, Pharmacol. Res., 7, 176, 1990.
2. Begley, I. H, Dennison, J. L, and Hollifield, H. C., Migration
into food of polyethylene terephthalate (PET) cyclic oligomers
from PET microwave packaging, Food Addit. Contam., 7, 797, 1990.
3. Linssen, G., Reitsma, H., and Cozynsen, G., Static headspace
gas chromatography of acetaldehyde in aqueous foods and polythene
terephthalate, Z. Lebensm. Untersuch. Forsch., 201, 253, 1995.
4. Eberhartlinger, S., Steiner, J., Washuttl, J., and Kroyer,
G., The migration of acetaldehyde from polythene terephthalate
bottles for fresh beverages containing carbonic acid, Z. Lebensm.
Untersuch. Forsch., 191, 286, 1990.
5. Piekacz, H., in Cz. II Ricz. Panst. Zakl. Hig., 22, 295, 1971
(in Polish).
6. Freire, M. T., Castle, L., Reyes, F. G., and Damant, A. P.,
Thermal stability of polyethylene terephthalate food contact materials:
formation of volatiles from retain samples and implications for
recycling, Food Addit. Contam.,15, 473, 1998.
7. Kashtock, M. and Breder, C. V., Migration of ethylene glycol
from polyethylene terephthalate bottles into 3% acetic acid, J.
Assoc. Off. Anal. Chem.,63, 168, 1980.
8. Komolprasert, V., Lawson, A. R., and Begley, T. H., Migration
of residual contaminants from sec . lary recycled poly(ethylene
terephthalate) into food-simulating solvents, aqueous ethanol
and heptane, Food Addit. Contam., 14, 491, 1997.
9. Fordham, P. J., Gramshaw, J. W., Crews, H. M., and Castle,
L., Element residues in food contact plastics and their migration
into food simulants, measured by inductively-coupled plasma-mass
spectrometry, Food. Addit. Contam., 12, 651, 1997.
10. Monarca, S., De Fusco, R., Biscardi, D., De Feo, V., Pasquini,
R., Fatigoni, C., Moretti, M., and Zanardini, A., Studies of migration
of potentially genotoxic compounds into water stored in pet bottles,
Food Chem. Toxicol., 32, 783, 1994.
11. Otaka et al., cit in Excerpta Medica, Sec. 17, 1, 1980, Abstract
284.
12. Bazanova, A. I., Effect of chemical substances extracted from
plastics on mammals and micro
organisms, in Toxicology and Hygiene of High-Molecular-Mass Compounds
and of the Chemical
Raw Material Used for Their Synthesis, Proc.3rd All-Union Conf,
S. L. Danishevsky, Ed., Khimiya,
Moscow-Leningrad, 1966, 113 (in Russian).
13. Kupyrov, V. N., Kaplina, T. V., Gakal, R. K., Vinarskaya,
E. I., and Starchenko, S. N., Hygienic evaluation of films intended
for the waterproofing of unit prefabricated swimming pools, Gig.
Sanit., 5, 91, 1978 (in Russian).
14. de Fusca, R., Monarca, S., Biscardi, D., Pasquini, R., and
Fatigoni, C., Leaching of mutagens into mineral water from polyethylene
terephthalate bottles, Sci. Total Environ., 90, 241, 1990.
15. Blagoeva, P., Stoichev, I., Balanski, R., Purvanova, L., Mircheva,
T. S., and Smilov, A., The testing for carcinogenicity of a polyethylene
terephthalate vascular prosthesis, Khirurgia, 43, 98, 1990 (in
Bulgarian).
source: Sheftel, VO. Indirect Food Additives and
Polymers: Migration and Toxicology. Lewis Publishers, Boca Raton,
FL, 2000. pp.1132-1134
|