DEGRADATION

MECANISM
 Rubber compounds can be degraded
by reactions with oxygen, ozone, light,
metal ions and heat
Degradation by oxygen and ozone
proceeds via different chemical
mechanism and results in different
effects on physical properties of rubber
 Oxygen degradation results in
hardening (SBR, NBR, CR, EPDM )
or softening (NR, IR, IIR) throughout
the rubber article
Rubbers that do not contain C=C
unsaturation are less sensitive to
oxidation than diene rubbers
 Ozone degradation results in
discoloration and eventual cracking
of samples
Ozone degradation is primarily a
surface phenomenon
Xem Phn ny
Mechanism of rubber
oxidation
Initiation

RH Shear, T
R* + H*
R-R Shear, T
2R*
R* + O2 ROO*
Propagation
ROO* + RH R* + ROOH
ROOH RO* + OH*
ROOH + RH ROH + R*
+H2O
RO* + RH ROH + R*
OH* + RH HOH + R*
Termination
ROO* + R* ROOR

RO* + R* ROR

R* + R* RR
 The key to the process is the initial
formation of a free-radical species.

At high temperatures and at large

shear forces, free radical formation
takes place by cleavage of carbon-
carbon and carbon-hydrogen bonds
 trace impurities present in the polymer
systems could account for the relative
ease of oxidation
Due to the high reactivity of free
radicals, only trace amounts of these
peroxides need to be present to provide
initiation of the oxidative chain process
The rate of peroxide decomposition
and the resultant rate of oxidation is
markedly increased by the presence
of ions of metals such as iron,
copper, manganese, and cobalt
ROOH + Fe2+ RO* + Fe3+ + OH-

ROOH + Fe3+ ROO* + Fe2+ + H+

It is important to control and limit the

amounts of metal impurities in raw rubber
 Probably an important pro-oxidant for
all rubbers is ultraviolet light
 Stabilization mechanism of
antioxidants
Five general modes of oxidation inhibition
are commonly recognized:
- Metal deactivators (EDTA)
- Light absorbers (ZnO, TiO2, C.B)
- Peroxide decomposers (Mercaptants,
thiophenol , other organic sulfur compounds)
- Free radical chain stoppers
- Inhibitor regenerators
 Termination of propagating radicals
during the oxidative chain reaction is
believe to be the dominant
mechanism by which amine and
phenolic antioxidant operate.
The resulting antioxidant radical is
more stable than the initial peroxy
radical and terminates by reaction
with another radical in the system
It is important that the level of
antioxidant be kept at the optimum,
since excess
antioxidant can result in a pro-oxidant
effect (A-H + O2 AOOH).
The secondary antioxidant react with
the hydroperoxide resulting in an
oxidized antioxidant and an alcohol
 Free radicals develop in a polymer
system and react with oxygen
yielding a free radical peroxy.
This free radical, in turn, reacts with
a C-H linkage yielding a peroxide and
another free radical. This is the
chain reaction which continues
until it is halted.
 It is generally agreed that
antioxidant-free radicals are not
reactive and are, thus, effective
chain stoppers.
 Methods of studying the
oxidation resistance of
rubber
Accelerated aging
DSC
TGA
Spectroscopic techniques
SEM techniques
Ozone and Antiozonant
Chemistry
Mechanism of ozone attack
on elastomers
Ozone reacts with double bond of
rubber to form ozonide (I).
These ozonide cleave as soon as
they are formed to give an aldehyde
or ketone and a zwitterion (carbonyl
oxide)
 Although the cracking of rubbers is related
to the reaction of ozone on the double
bond, it must be mentioned that ozone
reacts also with sulfur crosslinks.

These reactions however are much slower.

The reaction of ozone with di- and

polysulfides is
at least 50 times slower than the
corresponding reaction with olefins.
RSSSR + O3 SO2 + RSO2-O-SO2R
(+ H2O) 2 RSO2H