Heat Stabilizer
Stabilizers for polymers are used directly or by combinations to prevent the various effects such
as oxidation, chain scission and uncontrolled recombinations and cross-linkingreactions that are
caused by photo-oxidation of polymers. Polymers are considered to get weathered due to the direct
or indirect impact of heat and ultraviolet light. The effectiveness of the stabilizers against weathering
depends on solubility, ability to stabilize in different polymer matrix, the distribution in matrix,
evaporation loss during processing and use. The effect on the viscosity is also an important concern
for processing.
Heat stabilizers are mainly used for construction products made of polyvinyl chloride, for instance
window profiles, pipes and cable ducts. Light stabilizers, for instance HALS, are especially needed
for polypropylene and polyethylene. The environmental impact of stabilizers for polymers can be
problematic because of heavy metal content. In Europe lead stabilizers are increasingly replaced by
other types, for example calcium-zinc stabilizers.[1]
1Antioxidants
2Hindered amine light stabilizers
3UV absorber
4Antiozonant
5Organosulfur compounds
6See also
7References
8External links
Antioxidants
Antioxidants are used to terminate the oxidation reactions taking place due to different weathering
conditions and reduce the degradation of organic materials. For example, synthetic polymers react
with atmospheric oxygen.[2] Organic materials undergo auto-oxidizations due to free radical chain
reaction. Oxidatively sensitive substrates will react with atmospheric oxygen directly and produce
free radicals. Free radicals are of different forms, consider organic material RH. This material reacts
with oxygen to give free radicals such as R, RO, ROO, HO[1]. These free radicals further react
with atmospheric oxygen to produce more and more free radicals. For example, R + O2 ROO
ROO + RH ROOH + R [1] This can be terminated using the antioxidants. Then this reaction
comes to, 2R RR ROO + R ROOR 2ROO Non-radical products[1] Weathering of
polymers is caused by absorption of UV lights, which results in, radical initiated auto-oxidation. This
produces cleavage of hydro peroxides and carbonyl compounds. This is because of the weak bond
in hydro peroxides which is the main source for the free radicals to initiate
from. Homolytic decomposition of hydro peroxide increases the rate of free radicals production[1].
Therefore it is important factor in determining oxidative stability. The conversion of peroxy
and alkyl radicals to non-radical species terminates the chain reaction, thereby decreasing the
kinetic chain length.
Hydrogen-donating antioxidants (AH), such as hindered phenols and secondary aromatic amines,
inhibit oxidation by competing with organic substrate (RH) for peroxy radicals, thereby terminating
the chain reaction and stabilizing the further oxidation reactions[1].
At K17, ROO + AH -> ROOH + A At K6, ROO + RH -> ROOH + R [1]
Here K17 is larger than K6, therefore AH can be at low concentrations. At low concentrations AH are
more effective because the usual concentration in saturated plastic polymer range from 0.01 to
0.05% based on the weight of the polymer.
Benzofuranones is another most effective antioxidant, which terminates the chain reaction by
donating weakly bonded benzylic hydrogen atom and gets reduced to a stable benzofuranyl
(lactone)[1].
Antioxidants inhibit the formation of the free radicals thereby enhancing the stability of polymers
against light and heat.
Hindered amine light stabilizers
The ability of hindered amine light stabilizers (HALS or HAS) to scavenge radicals which are
produced by weathering, may be explained by the formation of nitroxyl radicals through a process
known as the Denisov Cycle. The nitroxyl radical (R-O) combines with free radicals in polymers:
R-O + R' R-O-R'
Although they are traditionally considered as light stabilizers, they can also stabilize thermal
degradation.
Even though HALS are extremely effective in polyolefins, polyethylene and polyurethane, they are
ineffective in polyvinyl chloride (PVC). It is thought that their ability to form nitroxyl radicals is
disrupted. HALS act as a base and become neutralized by hydrochloric acid (HCl) that is released
by photooxidation of PVC. The exception is the recently developed NOR HALS which is not a strong
base and is not deactivated by HCl.[3]
UV absorber
Main article: UV stabilizers in plastics
The UV absorbers dissipate the absorbed light energy from UV rays as heat by reversible
intramolecular proton transfer. This reduces the absorption of UV rays by the polymer matrix and
hence reduces the rate of weathering. Typical UV-absorbers are oxanilides
for polyamides, benzophenones for PVC, benzotriazoles and hydroxyphenyltriazines
forpolycarbonate.
Strongly light-absorbing PPS is difficult to stabilize. Even antioxidants fail in this polymer since the
polymer is electron-rich and behaves as antioxidant. The acids or bases in the PPS matrix can
disrupt the performance of the conventional UV absorbers such as HPBT. PTHPBT which is
modification of HPBT are shown to be effective even in these conditions.[4]
