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Institute of Polymers - BAS

Laboratory of Bioactive Polymers

Polymer Packaging and Food:


Migration of Substances

D. Paneva, N. Manolova, I. Rashkov

BG/05/B/F/PP-166054 www.e-fost.org
Contents:

Migration of substances from the packaging to food


– generalities

Legislation related to the migration of harmful substances to food

Analytical methods and mathematical models used to


study the migration to food

Particular examples for food contamination with substances


from the polymer packaging
Polymer additives
Residual monomers and oligomers
Other contaminants migrating from the polymer packaging
The term “migration” of undesirable substances in respect to
polymer food packaging is used to describe the two-way transfer of
substances in the system package-food-environment.

Schematic representation of diffusion processes occurring at the polymer-food (solution) interface


TWO TYPES OF MIGRATION ARE DISTINGUISHED:

overall migration
specific migration
(often referred to as
global migration)

the transfer of all components that


are able to migrate per unit area of the migration of only one
packaging material regardless of their component
toxicity or non-toxicity

One of the main criteria when choosing the packaging material is


that the levels and the toxicity of all its ingredients (stabilizers,
! plasticizers, antioxidants, colouring agent, etc.) will not result in
deterioration of the food flavour and to chronic damages
to the consumers’ health even if some migration takes place.
Legislation related to the migration of harmful substances to food

The requirements in terms of food safety and consumers’ health care are
one of the major priorities in the EU countries.

The decision for usage of particular polymer material for production of food packages
is based on compromises – it is estimated if the benefits of its application are more
than the risks for the human health.

The risks in the usage of a polymer material consist in the possibility of migration
of a part of the substances leading to deterioration of the quality of the food
product or increasing its toxicity at prolonged use.

There are legislative regulations in EU (called Directives) on materials and


articles intended to come into contact with food that establish the maximum
permitted concentrations of these substances, methods for their analysis,
as well as mathematical models for predicting their migration.
Legislation related to the migration of harmful substances to food

The EU Directives concerning migration of substances from the packaging


material into food could be divided into three categories:

(1) Directives applicable to all materials and articles;


(2) Directives applicable to one category of materials and articles;
(3) Directives related to individual substances.

The Framework Directive 76/893/EEC of November 26, 1976 replaced by


89/109/EEC of December 21, 1988 establishes two general principles:

(1) The principle of the “inertness” of the packaging material and the “purity”
of the food;

(2) The principle of “positive labelling”


Analytical methods and mathematical models used to study the migration to food

Does the material meet the requirements?

Polymer identification
Spectral methods (IR and NMR analyses)

Analysis of volatile Extraction


ingredients
(gas chromatography)
Transfer into volatile
Analysis of non-volatile
Alternative solvents:
ingredients test overall migration
(NMR, gas chromatography,
mass spectrometry, specific migration
liquid chromatography,
UV spectroscopy)
Prediction, Migration
modeling
Reaction products as
migrating components, Migration into fatty food
impurities simulant:
overall migration
Mutagenicity of the extracts specific migration
IR, UV and NMR – infrared, ultraviolet and nuclear magnetic resonance spectroscopy
General strategy for studying the migration of substances from the polymer packaging into food.
The alternative methods for studying are shown as well.
Particular examples for food contamination with
substances from the polymer packaging

Main contaminants that can migrate from a polymer packaging into food

additives included in residual monomers and


the packaging oligomers

other contaminants
(e.g., residual solvents,
pigments, other organic
compounds)

For foreseeing the possibilities these contaminants to be transported into food


it is necessary to precisely know the chemical structure and the physico-chemical
behaviour of all ingredients of the packaging in different media.
Particular examples for food contamination with
substances from the polymer packaging

additives included in an additive is a substance that is an auxiliary ingredient


the packaging for improvement of the physico-mechanical properties of
the polymers during their processing and use

Depending on their application, the additives can be divided into the following groups:

plasticizers,
antioxidants,
UV-stabilizers,
lubricants.

The major requirement in the case of food packaging is the additive in the plastic
from which they are fabricated to meet the requirements for “food purposes”.
Particular examples for food contamination with
substances from the polymer packaging

additives included in
the packaging
Antioxidants (stabilizers, anti-aging additives)
for prevention the
degradation of the polymers during their processing, storage and use

OH Most of the antioxidants are non-toxic and have a


(H3C)3C C(CH3)3 satisfactory stabilizing effect.

DBC is a substance, which is soluble in


CH3
fats-containing medium. It has been first used as
an antioxidative additive in food products (E321)
2,6-di-tert-butyl-p-cresol
(DBC)
DBC is used as antioxidant in polymer packaging
from high-density polyethylene
Particular examples for food contamination with
substances from the polymer packaging

additives included in
Antioxidants (stabilizers, anti-aging additives)
the packaging

R OH Irganox 1010
R C R, R = (H3C)3C C(CH3)3 tetrakis[methylene(3,5-di-tert-
butylhydroxy hydrocinnamate)]
R
methane

CH2 CH2 C O

OH O
(H3C)3C C(CH3)3 Irganox 1076
octadecyl 3,5-di-tert-butyl-
4-hydroxyhydrocinnamate
CH2 CH2 C O C18H37
O

They are used as antioxidants in plastics from


low-density polyethylene and polypropylene.
Particular examples for food contamination with
substances from the polymer packaging

additives included in
Antioxidants (stabilizers, anti-aging additives)
the packaging

Irganox 1076 (polypropylene, 1.5 h, 135 0С)


Irganox 1010 (low-density polyethylene, 1.5 h, 95 0С) R OH
5000 0С)
Irganox 1010 (polypropylene, 1.5 h, 100 R C R, R = (H3C)3C C(CH3)3
4500 R
Migrated amount (µ g/dm2)

4000
Irganox 1010 CH2 CH2 C O
3500
O
3000

2500

2000 OH
1500 (H3C)3C C(CH3)3

1000 Irganox 1076


500 CH2 CH2 C C 18H37
O
0
A B C D O
water skim chicken vegetable
milk broth oil

The rate of their migration into food depends on the polymer nature, antioxidant type
and the composition of the food product.
Particular examples for food contamination with
substances from the polymer packaging

additives included in Plasticizers


the packaging
Compound that is added to the polymer for facilitating its processing

The phthalic acid esters have been the most widely used plasticizers.

O C 2H5 approved for use as plasticizer in


COCH2CH(CH2)3CH3 the manufacture of food packaging
materials for food with high water content

COCH2CH(CH2)3CH3 the migration of phthalates depends


on pH of the soft drinks as well as on the
O C 2H5 nature of the used preservative
di-2-ethyl hexyl phthalate or dioctyl phthalate

phthalates harm the liver;


!
they can cause weight loss, abortion, and birth of dead or prematurely born children;
they have toxic, carcinogenic, mutagenic and teratogenic effect;
phthalates imitate the estrogens, thus rendering harmful effect on the male sex glands.
Particular examples for food contamination with
substances from the polymer packaging

additives included in ca. 90% of all plasticizers are used with PVC
the packaging

The copolymers of poly(vinyl chloride) and poly(vinylidene chloride)


are plasticized with up to 5% of acetyltributyl citrate.
CO O (CH2)3 CH3
CH3 (CH2)3 O CO CH2 C CH2 CO O (CH2)3 CH3
O
CO
CH3
Migration of acetyltributyl citrate into microwave-cooked foods
Particular examples for food contamination with
substances from the polymer packaging

additives included in
the packaging Other types of additives

ethoxylated fatty acid, polyhydrated alcohols, non-ionogenic


antistatic agents substances that contain quaternized ammonium groups

“antifog” agents fatty acid esters (glycerol stearate and sorbitol stearate);
content: 0.5 – 4 %

stearamide, calcium stearate, alkylamines or quaternized


antiblocking agents alkylamine compounds;
quartz, clays, starch and silicones;
content: 0.1 – 0.5 %

activated carbon, titanium dioxide (imparts white colour),


dyes and pigments iron oxide (red colour), cadmium sulphide (yellow colour),
molibdates (orange colour), ultramarine blue, ferric
ammonium ferrocyanide (blue colour), chrome green,
and blue and green copper phthalocyanine.

foaming or blowing agents СО2 or aliphatic hydrocarbons (for example, pentane)


Particular examples for food contamination with
substances from the polymer packaging
The monomers are much more toxic than the
residual monomers and
corresponding polymers
oligomers
Polystyrene is widely applied in the fabrication of packaging for
yoghurt, water, hot and cold drinks, oil.
It has been found that the migration of styrene from polystyrene
cups containing hot or cold drink is about 0.025% per cup.
CH CH2
the product of styrene metabolism – styrene oxide,
is a mutagen.
!!
styrene acts as a depressant (it causes neurological
diseases) and is harmful for the liver.
styrene
styrene vapours cause irritation of eyes, nose, throat, and skin.

in the human body styrene simulates the estrogens, and therefore


could harm the normal functions of the hormones (problems with
the thyroid gland, unregulated menstrual cycle and other
hormones-related problems, including breast and prostate cancer)

The higher the fat contents, the higher the migration of styrene into food.
Particular examples for food contamination with
substances from the polymer packaging
residual monomers and
oligomers
!

CH2 CH highly toxic substance - its levels in poly(vinyl chloride)


food packaging materials are controlled extremely strictly

Cl
Any package that contains 275 ppb residual vinyl chloride
vinyl chloride cannot be used for food applications!!!

comonomer which presents in several copolymers used as


CH2 CH food packaging materials; in terpolymers containing styrene
or butadiene its content may reach up to 70%
CN
In 1975, a regulation that limited residual monomer levels to
80 ppm in the wall of the bottle has been published and
acrylonitrile enacted that monomer migration into the food product
could not be greater than 0.3 ppm.
Particular examples for food contamination with
substances from the polymer packaging

other contaminants
Due to the complex structure and chemical composition of the
(e,g, residual solvents, packaging materials, it is possible during their processing
pigments, other organic and use different reactions to occur that
compounds) could result in obtaining of harmful substances,
which at a next stage could
migrate into the food product.

The identification and analysis of the obtained


substances migrated into the food
product is a very difficult task.

Systematic studies on each system polymer packaging material – food product


is necessary to be conducted.

The most modern trend - replacement of the most of the components


(main polymer, plasticizers, stabilizers, colouring agents) in the packaging
! material with natural and non-toxic for the human health substances.
Such type of replacement will lead to obtaining of polymer material that
will not release toxic substances into the food product, and subsequently the
risk for the human health will be drastically reduced.
Acknowledgments:
BG/05/B/F/PP-166054 www.e-fost.org
Bulgarian Academy of Sciences
Institute of Polymers
N. Manolova, O. Stoilova, D. Paneva, I. Rashkov
Polymeric materials from synthetic and natural
polymers for food packaging and food
preservation
Leonardo da Vinci II
Specific content issues in:
e-Reference Tools for VET Trainers in Food Industry
Pilot project

Grant ТК CH 1605
Novel functional nanostructured materials for
electrochemical detection of pesticides in foods
THANK YOU FOR THE ATTENTION!