Workshop 2 - Food Packaging and Use of Stabilizers

ADVANCED BIO-FRIENDLY POLYMERS
Food packaging and use of stabilizers
Gyrgyi Szarka
Packaging materials
Paper
Metal
Plastic:
-PP
-PET
-PS
-PVC
-Polyesthers
-PE
box
foil
light,
transparent,
unbreakable,
minimal use of material,
good gas and aroma closing,
valuable raw material
http://www.foodpackagingforum.org/Food-Packaging-Health/Food-Packaging-Materials
C. Silvetre et. al. Prog. Polym. Sci., 36, 2011, 1766 .
Polymer additives
FUNCTIONAL
Plasticizer
Lubricant
Antistatic
Filler
Foaming / Crosslinking
Colorant
Flame retardant
PROTECTING
Heat stabilizer
Light stabilizer
Antioxidant
TYPICAL STABILIZERS
Primary stabilizers/ antioxidants:
Hindered phenols, aromatic amines
Secondary stabilizers / peroxide
decomposers:
Organic thioesters, phosphites and metalthiocarbamates
Chelating agent/metal deactivator:
Organic phosphites and hydrazides
Problem related to food packaging
Migration of additives
Chemical changes during processing
Health problem due to synthetic
stabilizers
FOOD
FOOD
FOOD
Strategies to avoid migration
Macromolecular stabilizer
grafting by chemical decomposition of 1,2,2,6,6-pentamethyl-4piperidyl-acrylate (PMPA)
Connect the stabilizer to the polymer (grafting / copolymerization )

1. time antioxidant used in
copolymerization with olefin
under Ziegler-type conditions
M. L. Binet, S. Commereuc, P. Lajoie, J. Lacosta, J. Photochem. Photobiol. A: Chem., 137, 71, (2000)
T.L. Pattorn, J. T. Horeczy, D. E. Brown (to Esso Research and Engineering Co.) U. S. 3,477,991 (1969 )
T. Iwata, J. Sasaki (to Mitsui Petrochemical Co., Ltd), Canadian 876,769 (1971)
Changes during processing
Manufacturer should guarantee not only the safe use of the additive but the product(s) of
them after processing
There are some health concern in relation to BHT, the quinone form causes lung cancer in
mice. Human health problem has not been proved yet.
Natural materials in packaging

Environmental and health problem due to synthetic stabilzers
Natural antioxidant: lignin, carotin, quercetin
Radical scavenger: vitamin E
carotin
vitamin E
quercetin
BIODEGRADABLE POLYMERS:
PHA, PHB, PLA
(Ecoflex, Ecovio)
1. Brocca, D.; Arvin, E, Mosbaek, H: Water Res., 36, 3675-3680, 2002

2. Pataki P., Imra B., Fldes E., Puknszky B., Manyag s Gumi, 2012, 1
1935/2004/EC regulation
This Regulation covers all materials and articles that are intended to
come into contact with food: all types of packaging, bottles (plastic and
glass), cutlery, and even adhesives and inks for printing labels.
They must under no circumstances transfer substances to the food with

which they are in contact in quantities likely to:
endanger human health;
bring about an unacceptable change in the composition of the food; or
bring about a deterioration in the organoleptic characteristics thereof.
Active materials and articles: intended to come into contact with food:
materials and articles that are intended to extend the shelf-life or to maintain
or improve the condition of packaged food. They are designed to
deliberately incorporate components that would release or absorb
substances into or from the packaged food or the environment surrounding
the food.
Intelligent materials and articles intended to come into contact with food:
materials and articles which monitor the condition of packaged food or the
environment surrounding the food.
Active and intelligent material
Oxygen absorbents: ascorbic acid, metal-sulfides, glucose oxidase,

catalase enzyme, amorphous polyamide
Oxygen exclusion: ethylene/vinyl alcohol closing coating

with Fe-compound
Water vapour absorbents: molecular sieve, silica, CaO, Al coating
Moisture controller: salts
Antimicrobial packaging: sorbic acid, Ag
Summary
The use of plastics is rapidly expanding in food
packaging industry
The new products are more sophisticated and fit
better to the improved claims with special
polymers and active additives
These materials should improve not only the
physical, chemical but the health safety
properties of the package (EU) due to
- reducing migration
- and full controll of all the used
materials and evolved products
during
processing
Macrostabilizer strategy
Compatibilizer
Hyperbranched
polymer
Stabilizers
Acknowledgement
HUSK /1101/1.2.1/0209
Hungarian Academy of Sciences

Research Centre for Natural Sciences
Institute of Materials and Environmental Chemistry
Department of Polymer Chemistry
Packaging
Barrier protection - A barrier from oxygen, water vapor, dust, etc., is often required.
Permeation is a critical factor in design. Some packages contain desiccants or
Oxygen absorbers to help extend shelf life. Modified atmospheres or controlled
atmospheres are also maintained in some food packages. Keeping the contents
clean, fresh, and safe for the intended shelf life is a primary function..
Convenience - Packages can have features which add convenience in distribution,
handling, stacking, display, sale, opening, reclosing, use, and reuse.
Macromolecular stabilizers
Advantages
Very low migration to the surface
Long and predictable effect
Properties (eg. solubility, miscibility) can be
easily modified by molecular weight and
functionality
Disadvantages
Further functionalization reactions, which are
often expensive and time consuming
INTERPACK 2011
Other additives
Antiaging additives:
BHT has been cleared by the FDA
MULTIFUNCTIONAL HYPERBRANCHED
POLYMERS
repetitively branched molecules start-up of one well defined
Dendrimers:
central core
low viscosity
high chain-end funcionality
developing of generations can be made by only
expensive, difficult and time consuming methods
and reactions
Hyperbranced polymers:
no special main chain
statistical distribution of branch points
The branched polymers have all the
beneficial properties of dendrimers.
Synthesis: different one-step reactions
Polycondenzation of ABn-type
monomers
Sequential grafting
INIMER POLYMERIZATION
Self-grafting of polymers
HYPERBRANCHED
POLYGLYCEROL
Properties
Synthesis: cationic or anionic Ring Opening Polymerization of
glycidol
OH
OH
O
O
Core
OH
base
slow monomer
addition
Core
O
O
O
HO
OH
OH
OH
OH
O
HO
OH
Well defined product (Mn, PD, number of OH-groups)

Good solubility in water
OH-groups can be functionalized easily
Biocompatible
does not induce an immune response
oligomers are FDA approved for food and pharmaceutical
THE TARGET STABILIZER

OH
OH
O
OH
O
O
O
O
O
OH
OH
OH
O
O
OH
OH
OH
OH
OH
O
O
OH
O
O
O
OH
O
OH
OH
STABILIZER
COMPATIBILIZER
Effect
of
antioxidant
Stabilization of chain-breaking antioxidants
Stabilization by preventive (secondary) antioxidants

phosphites, organic sulfides
Effect of heat stabilizer
The processing temperature is about 180-200 C.

ROOH + Mn+
ROOH + M(n-1)+
ROO. + M(n-1)+ + H+
RO. + Mn+ +OH-
Mn+/M(n-1)+
2ROOH
ROO. + RO. + H2O
Much more efficient inhibition is achieved by using

metal deactivators, together with the antioxidants.
Effect of light stabilizer
Small amounts of impurities or chromophores can be sufficient to induce

photooxidaiove degradation even in the absence of appreciable UV absorption
by a polymer.
Types:
UV absorbers: absorption of harmful UV radiation and it dissipation that does
not form heat. Need a thickness. Hxdroperoxybenzophenones and
hydroxyphenyl benzotriazoles.
Quenchers of excited states: light stabilizers able to take over energy
absorbed by the chromophores present in the plastic and to dispose of it
efficiently to prevent degradation.
Hydroperoxide decomposers: metal complexes of sulfur-containig
compounds such as dialkyldithiocarbamates, dialkyldithiophosphates and
thiobisphenolates.
Free radical scavengers: n-butylamine-nickel-2,2-thio-bi-(4-tert.octylphenolate) nickel-bis(3,5-di-tert.-butyl-4-hydroxybenzol-phosphonic acid
monobutylester). Hindered amine typelight stabilizers: bis(2,2,6,6-tetramethyl4-piperidyl) sebacate.
Food packaging and use of stabilizers

Gyrgyi Szarka, Bla Ivn
Department of Polymer Chemistry

Institute of Materials and Environmental Chemistry
Research Centre for Natural Sciences, Hungarian Academy of Sciences

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ADVANCED BIO-FRIENDLY POLYMERS

Food packaging and use of stabilizers

Problem related to food packaging

Strategies to avoid migration

Connect the stabilizer to the polymer (grafting / copolymerization )

Changes during processing

Natural materials in packaging

1. Brocca, D.; Arvin, E, Mosbaek, H: Water Res., 36, 3675-3680, 2002

They must under no circumstances transfer substances to the food with

Active and intelligent material

Oxygen absorbents: ascorbic acid, metal-sulfides, glucose oxidase,

Oxygen exclusion: ethylene/vinyl alcohol closing coating

Hungarian Academy of Sciences

Well defined product (Mn, PD, number of OH-groups)

THE TARGET STABILIZER

Stabilization by preventive (secondary) antioxidants

Effect of heat stabilizer

The processing temperature is about 180-200 C.

ROO. + RO. + H2O

Much more efficient inhibition is achieved by using

Effect of light stabilizer

Small amounts of impurities or chromophores can be sufficient to induce

Food packaging and use of stabilizers

Department of Polymer Chemistry

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