CH 2 - C = CH
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Transcript CH 2 - C = CH
CHEMICAL DEGRADATION
Whilst all polymers will be attacked by certain
chemicals it is the reactive chemicals in the
atmosphere which must be considered.
Of these probably the most important are:
1) Oxygen which leads to oxidative degradation.
2) Ozone - which leads to ozonolysis
3) Water
- which leads to hydrolytic
degradation.
Protection
A range of ANTIOXIDANTS etc. Have been
developed. Combinations of antioxidants often
used to obtain a synergistic effect.
OXIDATIVE DEGRADATION
Oxidative degradation normally initiation by
1) radiation e.g. UV
2) heat
3) direct O2 attack (not too important with
saturated polymer)
4) initiator residues (proxides).
UNSATURATED POLYMERS
1) Can be easily initiated
2) Can be sujected to repeated O2 attack
3) Must always be protected
- CH2 - C = CH - CH2
CH3
H2 allylic hydrogen’s – easily replaced
- CH2 - C = CH - CH
CH3
- CH2 - C - CH = CHCH3
PROTECTION
By preventing the production of free radicles.
MECHANISMS
1- system which cross-link.
Example
Polyethylene.
Changes observed on exposure to radiation are:
a) H2 and low molecular mass hydrocarbons
evolved.
b) cross – linking occurs.
c) unsaturation Increases.
d) crystallinity decreases.
e) polymer yellows.
f) in air surface oxidises.
hv
-----CH2--------
----CH------ + H
H + ----CH2----
----CH------ + H2
H + ----CH2----
----CH------ + CH4
CH3
branch
----CH------ cross – link forms
2 ----CH----
----CH------ by radical combination
H
H
----CH--CH------CH---- + O2
hv
unsaturation increases
----CH = CH---- + H2
----CH------
ocidative
----O – O ----- breakdown
2- System which show reduction in molecular
mass.
Mechanism still obscure, two main theories
a) fracture of main chain followed by
disproportionation of radicles.
CH3
CH3 hv
----CH2 – C - CH2 – C CH3
CH3
CH3
CH3
+
CH3
----CH2 – C + CH2 – C -----
CH3
CH2
----CH2 – C
CH3
CH3 – C ---CH3
CH3
disproportionation
B) Multiple bond scission
CH3
----CH2 – C
CH3
hv
complex rearrangement.
OXIDATIVE DEGRADATION
MECHANISM
Initiative:- Formation of free radicales.
e.g. from catalyst residue, effect of radiation and heat.
Propagation: radical formed on polymer chain as
consequence of initiation step (Ro) is attacked by oxygen.
R
+
O2
ROO
ROO
+
RH
ROOH + R
RO
+ OH
Hydroperoxide
decomposition
Rearrangement to stable product
i.e. termination
example
Saturated polymer (polystyrene)
----CH2 - CH --CH2 – CH-
hv
----CH2 - C
--CH2 – CH---
O2
O-O
----CH2 – CH----
OH +O
----CH2 – C-- -------CH2 – C-- ---
rearrangement
----CH2 - CH
O OH
----CH2 – C-- --- + ----CH2 – C-- --ROOH
hydroperoxide
Farther chain
activated
Chain
rearrangement
scission
O
----CH2 - CH
OH
+
----CH2 – CH--
Stable products
OXIDATIVE DEGRADATION
Unsaturated polymer
Effect of oxygen attack far more serious
with unsaturated polymers
e.g. natural rubber.
MECHANISM
CH3
CH3
--------CH2 – C = CH – CH2 - CH2 – C = CH – CH2---------
-H
CH3
CH3
--------CH2 – C = CH – CH2 - CH2 – C = CH – CH--------Rearrangement to stablilise radical
CH3
CH3
--------CH2 – C = CH – CH2 - CH2 – C - CH = CH--------O2attack
CH3
CH3
--------CH2 – C = CH – CH2 - CH2 – C - CH = CH--------Hydroperoxide
cyclization
O-O
formation
CH3
CH2 – CH2
--------CH2 – C - CH
CH3
C - CH = CH---------
O-O
further O2attack
CH3
CH2 – CH2
CH3
--------CH2 – C - CH
C - CH = CH--------Further
O-O
O-O
cyclization
Hydroperoxide formation
CH3
CH2 – CH2
--------CH2 – C - CH
HO - O
O-O
CH3
C - CH = CH---------
Hydroperoxide decomposition
CH3
CH2 – CH2
--------CH2 – C - CH
HO + O
O-O
CH3
C - CH = CH---------
Chain scission
CH3
H - C – CH2 - CH2 – C - CH = CH-----O
O
Further chain scission
CH3
+
CH2 - C –
O
CH3
H - C – CH2 - CH2 – C
O
O
+
CH = CH-----To stable
product
ANTIOXIDANTS
It is a must in some way to stop the
breakdown process.
1- inhibitors
2- light absorbers
3- hydroperoxide decomposing agents
4- propagation interrupturs.
5- metal deactivators
INHIBITORS
React rapidly with radicals, therefore it
stops the initiation stage.
Example
Benzoquinone
R
+
O
O
hv
RO
LIGHT ABSORBERS
Again prevent initiation caused by
radiation.
Example
2 hydroxybenzophenones
H
O
O
hv
C
H
O
C
O
HYDROPEROXIDE DECOMPOSING
AGENTS
Example
Sulphides.
R2S + ROOH
R2SO + ROH
PROPAGATION INTERRUPTURS
Example Phenols and amines
OH
tBu
tBu
+ ROO
CH3
2, 6 – ditertiary butyl 4 methyl phenol
O
tBu
+
ROOH
tBu
CH3 OOR
CH3
O
O
tBu
tBu
+
ROO
tBu
tBu
CH3
METAL DEACTIVATORS
Multivalent metal ions accelerate oxidation and
generate the unwanted peroxy radical.
This must be prevented by complexing out the
metal ions using chelates.
If this is not done the hydroperoxide breakdown
is accelerated and occurs as shown below.
M2+ +
M3+ +
ROOH
ROOH
Overall 2 ROOH
M3+ + RO + OHM2+ + RO O + H+
RO
+ RO O
+ H+
Thank You
See You Next Lecture