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Antioxidants:
primary (chain-breaking) interfere with the chain propagation step
secondary (preventive) destroy hydroperoxide groups
Stabilization by chain-breaking
antioxidants
Two reaction mechanisms by which antioxidants interfere
with chain-carrying radicals:
Chain-breaking donor mechanism (CB-D)
phenols, disubstituated phenols,
secondary aromatic amines
Chain-breaking acceptor mechanism (CB-A)
quinone-type compounds
stable free radicals: e.g. piperidinoxyl-compounds
Chain-breaking donor mechanism (CB-D)
The radical abstract a H atom from the inhibitor (AH) which is
transformed into the radical (A) which can interact with another peroxy
radical:
O HO
CH3 C18H37
O 2
NH NH
NH NH
H3C CH3
S C18H37 S
C18H37 S
OH HO
O
H N O O
(CH2)8 P O C9H19
O N H 3
Commercially used antioxidant
O O
Effect of catalyst residues and metal
contamination
In the presence of catalytic amounts of certain metal ions, hydroperoxides
decompose already at room temperature by a redox mechanism into
radical products:
The most active catalysts: derivatives of those metals, which are easily
oxidized or reduced by one-electron transfer and have different oxidation
state: Fe, Co, Mn, Cu, V, Ti (transition metals)
Mechanism:
Hindered Amine
Light Stabilizers (HALS)
Free radical scavenger
Does not absorb any light above 250 nm
peroxy radicals can react very quickly with hydroxylamine ethers and
regenerate nitroxy radicals
FUNDAMENTAL PROBLEM
FOIL
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
Macromolecular additives in the
market
Light stabilizer
(Ciba) UV and long term heat
stabilizer (Vanderbilt)
THANK YOU FOR YOUR
ATTENTION!
Thermal, antioxidative and photochemical
stabilization of polymers:
low molecular weight versus
macromolecular stabilizers
György Kasza
Department of Polymer Chemistry, Institute of Materials and Environmental Chemistry
Research Centre for Natural Sciences, Hungarian Academy of Sciences
DEGRADATION OF POLYMERS
POLYFRIEND Educational Course
September 5, 2013
Bratislava, Slovakia