ADVANCED BIO-FRIENDLY POLYMERS

Photo degradation of polymers

Štefan Chmela
One of the disadvantages of using polymers in high temperature
conditions or in outdoor applications – degradation
environment negatively influences the service life.

This process is called weathering - ageing

an irreversible chemical process,

undesired changes of properties of the polymers,
discoloration and loss of mechanical properties.

outdoor applications -reactions of the polymer with and without

oxygen induced by terrestrial sunlight

the UV-radiation is one of the most important factors determining

the polymers lifetime.
 Solar irradiance spectrum above atmosphere and at surface.

Sunlight in space at the top of Earth’s atmosphere at a power

of 1366 watts/m2 is composed (by total energy) of about 50%
infrared light, 40% visible light, and 10% ultraviolet light.
Ultraviolet C or (UVC) range, which spans a range of 100 to 280 nm.
The term ultraviolet refers to the fact that the radiation is at higher
frequency than violet light (and, hence also invisible to the human
eye). Owing to absorption by the atmosphere very little reaches the
Earth's surface. This spectrum of radiation has antiseptic properties
and is used in germicidal lamp.

Ultraviolet B or (UVB) range spans 280 to 315 nm. It is also greatly

absorbed by the atmosphere, and along with UVC is responsible for
the most of photochemical reactions.

Ultraviolet A or (UVA) spans 315 to 400 nm.

 Degradation due to UV-radiation is called photodegradation.
Chemical reactions -chain scissions,
- cross linking
- oxidation
influence the physical properties and thus the article's lifetime

Besides the service environment, other parameters, as the polymer

itself and the use of stabilizers influence the rate of degradation.

The most important polymer-related parameters for degradation

are the type of polymer, (e.g. polyolefins, engineering plastics as
polyamides or polycarbonates), the amount of branching, catalyst
residues, or end groups.

Different techniques to stabilize polymers have been developed,

e.g. adding different types of stabilizers, or applying a protective
coating
light is absorbed by a polymer - photochemical reactions can occur as a
result of activation of a polymer macromolecule to its
excited singlet or triplet states
precursors of all photochemical reactions

The most important mechanisms causing weathering of polymers are

photolysis and photooxidation.

If the absorption of light leads directly to chemical reactions causing

degradation, this is called photolysis.

Photo-oxidation is a result of the absorption of light that leads to the

formation of radicals that induces oxidation of the material.

oxidation products are distributed non-homogeneously in the sample

 photo-oxidation
polyolefines (PE, PP) = photo-oxidation is the dominating
mechanism.
These polymers do not have an inherent absorption at wavelengths
present in terrestrial sunlight (>290-400 nm)
photolysis can not play an important role.

Nevertheless, irradiation of these polymers with terrestrial

wavelengths results in accelerated degradation – especially for PP

This can be ascribed to impurities that are formed during storage

and processing.

Due to photolytic reactions of these absorbing species, radicals are

formed that initiate the photo-oxidation reaction.
 impurities responsible for the initiation

Hydroperoxide >> carbonyls > unsaturations

> complex [PH...O2], atmospheric impurities (SO2, NO), aromatic
hydrocarbons, singlet oxygen

Main steps of photo-oxidation

Initiation
Propagation
Branching
Termination
Iniciácia:

R H .
R (1.1)
R R

Propagácia:
. ROO
. (1.2)
R + O2
. . (1.3)
ROO + RH ROOH + R
.
RO
. + RH ROH + R (1.4)
. OH H2O +
.
R (1.5)
+ RH

.
R + C C R C C. (1.6)
.
O O
-štiepenie . (1.7)
R
1
C R
2 1
R C R2 + R3
R3
. fragmentácia ,. (1.8)
R olefín + R

Vetvenie:
. . (1.9)
ROOH RO + OH
. . (1.10)
2 ROOH RO + ROO + H2O

Terminácia:
. + ROO . ROOR (1.11)
R
. . R R (1.12)
R + R
. RO
. R O R (1.13)
R +
. disproporcionácia RH + olefín (1.14)
2R
O OH
.
2 ROO ROO + ROO + O2 (1.15)
In contrast to polyolefins, the majority of engineering plastics
e.g. aromatic polyesters, polyamids, polyuretanes, polycarbonates, polyketones
etc.)
do have absorptions
at wavelengths being present in terrestrial sunlight, so that for these polymers
photolysis can play an important role too.

For these polymers in principle there are three mechanisms that can describe
their light-induced degradation:

• Photolysis - absorption as a result of the inherent polymeric structure results

in chemistry causing changes in the molecular structure;

• Photo-oxidation initiated by photolysis reactions of the polymer itself;

• Photo-oxidation initiated by impurities not part of the inherent polymer

structure.
 Photolysis: Norrish I, Norrish II
When light is absorbed by the polymer, Norrish reactions can occur, which lead to
changes in molecular structure resulting in degradation. The Norrish I reaction
leads to chain cleavage and radicals that might initiate the photo-oxidation.
The Norrish II reaction is a non-radical intramolecular process, in
which hydrogen (hydrogen on gama C), is transferred, leading to
chain cleavage.

For polyamides and polyesters (biodegradable polymers) the most

important photolytic reactions are the Norrish I and II reactions.
 photo-Fries reactions

phenyl ester reaction, production of more photoactive ketone

photo-Fries rearrangement may occur naturally, for example when a plastic bottle made of
polyethylene terephthalate (PET) is exposed to the sun, particular to UV light at a
wavelength of about 310 nm.
Radical oxidation process of irradiated PLA samples: hydroperoxide chain propagation
and formation of anhydrides by photolysis of hydroperoxide
 General scheme for degradation and stabilization
PH
PH - O2
PH
MECHANICAL

S/X h, ,M
n+ ..
S /X
STRAIN
h
3
O2

PH
LIGHT SCREENING
S/X P-P
UV ABSORBERS

CH CH *
PH P
. DISPROP
.
PO2
h

PH
3O
QUENCHER 2
.
PO
n+1
h,M
1O
2 PH
POOH PH

METAL HYDROPEROXIDE RADICAL

DEACTIVATOR DECOMPOSER SCAVENGER
 Testing methods
Natural ageing
Artificial ageing

Changes are followed by

spectral methods (FTIR, UV-Vis, fluorescence)

GPC – molecular mass
mechanical properties
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Direct Setting and Control of Irradiance in the wavelength range 300-800 nm / Lux; or
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Direct Setting and Control of Black Standard Temperature (BST)
Display of Chamber Air Temperature
Display of Test Values and Diagnostic Messages
Parameter Check
Two pre-programmed test methods
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Direct Setting and control of Irradiance: 340nm, 420nm, 300-400nm or Lux
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Example of testing new stabilizer
Additives: processing sterically hindered phenols
phosphites
long term stabilizers UV absorbers
Hindered Amine Stabilizer - HAS

Usually the mixture of low molecular weight additives are used.

Advantage possible synergistic effect

Disadvantages possible antagonistic effect

physical loss during processing – evaporation (high
temperature)
during long term application - washing out

Solving the problem - synthesis of combined higher molecular

weight additives

Combination of phenol/HAS
Monitoring of photo-oxidation by FTIR spectroscopy
 Changes of FTIR spectra of PP film during irradiation

0,5 0,6

600 hrs
pure iPP 0,5
0,4 pure iPP

0,4
OH absorptions

0,3 600 hrs

CO absorptions
535 hrs
0,3
535 hrs
0,2

490 hrs 0,2

490 hrs
0,1

0 hrs 0,1 0 hrs

0,0

0,0

-0,1
3700 3600 3500 3400 3300 3200 1800 1700 1600
-1 -1
, cm , cm

Changes of the carbonyl region

Changes of the –OH vibrational region
 0.5
PP powder fresh
0.4 pure PP
Carbonyl Absorption TMP-I
TMP-II HO NH
0.3
TMP-III
TMP-IV
0.2

Ph O NH CH3
0.1
O
NH X HAS
0.0
0 500 1000 1500 2000 2500 3000 3500 4000 4500 O
Irradiation time (h)

CH3 O OH OH OH OH
0.5
I II III IV
0.4
pure PP
Carbonyl Absorption

PMP-I
0.3 PMP-II
PMP-III
PMP-IV
0.2

HO N CH 3
0.1

0.0
0 500 1000 1500 2000 2500 3000 3500 4000

Irradiation time (h)

Thank you for your attention