Recent progress in the field of polymer photodegradation

Jean-Luc Gardette, Pierre-Olivier Bussière, and Sandrine Therias

Citation: AIP Conference Proceedings 1981, 020051 (2018); doi: 10.1063/1.5045913

View online: https://doi.org/10.1063/1.5045913
View Table of Contents: http://aip.scitation.org/toc/apc/1981/1
Published by the American Institute of Physics
 Recent Progress in the Field of Polymer Photodegradation
Jean-Luc Gardette, Pierre-Olivier Bussière, Sandrine Therias

Université Clermont Auvergne, Institut de Chimie de Clermont-Ferrand,

UMR 6296 CNRS / UCA / Sigma Clermont – 24 Avenue Blaise Pascal, 63178 Aubière, France
luc.gardette@uca.fr

Abstract. Weathering of polymers has been the subject of intensive scientific research over the past 40 years. In addition
to the academic interest for understanding the mechanistic behaviour of polymers, developing and adapting rational
strategies to improve material performance and predicting the service life of polymers are most valuable for practical
applications of polymeric materials. This talk focuses on the fundamental and technical aspects of polymer weathering,
with a special emphasis to the issues dealing with photodegradation. It gives an overview of the main principles that
govern photodegradation of polymeric materials.
Keywords: polymers; light; photochemistry; spectroscopy; chemical reactions
PACS: 82.50.Hp; 81.05.Lg; 81.70.Jb

INTRODUCTION
It is now well admitted that, in outdoors weathering conditions, most of the properties degradation results from
chemical changes of the macromolecules. In a majority of cases, the main cause of property deterioration is
photooxidation, which is initiated by light irradiation. Radiation in the ultraviolet and visible is indeed the primary
factor in outdoor polymer weathering. Effects from heat, moisture, pollutants, mechanical stresses, and biological
attack can come into play, but in many cases the weathering process begins with a photochemical event. Solar UV
light induces photochemical processes in organic materials, which result in fixation of oxygen, rearrangements,
chain scissions, cross-linking, photo-discoloration and photo-bleaching. All these processes contribute to a decrease
of the various properties of the materials, such as physical, mechanical, barrier, aspect, electrical… properties.
Despite the very large effort put into the development of mechanical and chemical methods for assessing
degradation, there are still gaps in the understanding of the links between chemical reactions and engineering failure
in weathered polymers. The main difficulty consists in establishing the relationships between the successive levels
of investigation: chemical analysis at the molecular scale, characterization of local mobility and organization,
investigations at the nanometric scale of the associations of macromolecules, investigations at the microscopic level,
and investigations at the macroscopic scale with the degradation of the use properties of the polymeric material.
Consequently, complementary concepts are needed in order to study the complex phenomena involved in the
degradation of polymers. Because no experimental simplification could be made, the development of new concepts
is required, with novel experimental procedures and analytical techniques.
This presentation will focus on the basic aspects of polymer photodegradation through the examination of the
photochemical mechanisms of polymers of interest in several domains of applications currently investigated.

MECHANISMS OF PHOTOCHEMICAL DEGRADATION

The wavelengths of the radiation from the sun that reaches the surface of the earth extend from the infrared to the
ultraviolet with a cut-off around 300 nm depending on the atmospheric conditions. The quantum energies associated
with wavelengths in the region 300-400 nm are sufficient to break chemical bonds in most polymers. Of course, the
basic law of photochemistry tells that only the light absorbed by a system is effective in producing a photochemical
change. This means that the presence of chromophoric groups is required to absorb the incident radiation.
9th International Conference on “Times of Polymers and Composites”
AIP Conf. Proc. 1981, 020051-1–020051-4; https://doi.org/10.1063/1.5045913
Published by AIP Publishing. 978-0-7354-1697-0/$30.00

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 If one considers the chemical structure of a number of aliphatic polymers (PE, PP, EPDM, EVA, …), no
absorption in the range of sunlight spectrum (λ > 300 m) is expected. Yet these polymers are susceptible to
photodegradation to some extent1,2. Photo-oxidation of so-called “non-absorbing” polymers starts with light
absorption by a chromophor that is not a feature of the basic polymer. The discussion on the initiation of
photodegradation of "non-absorbing" polymers has been the subject of many papers. The true nature of the
chromophores responsible for photoinitiation of the degradation is not unambiguously established, and probably
never will be. The fact that the transparent polymers are susceptible to absorb light results from the presence of
chromophoric impurities. The chemical nature and the relative importance of these chromophores depend essentially
on the thermal history of the polymer: conditions of polymerisation, processing and storage.
At opposite, the photosensitivity of many aromatic polymers, such as polycarbonate, polyethyleneterephthalate,
polyurethanes...3 is attributable to their strong inherent UV absorption above 300 nm. In the case of these “light-
absorbing” polymers, light absorption then comes from a chromophor that is part of the macromolecular chain.
Let’s consider a few examples to illustrate the fate of “non-absorbing” and “absorbing” polymers.

“Non-Absorbing” Polymers: The Example of Polyvinyl Alcohol (PVA)

Polyvinyl alcohol (PVA) is a water-soluble polymer used in various field due to its biodegradability, oxygen
barrier property and environmentally friendly processing. Transparent flexible self-standing films of PVA can be
easily obtained through the evaporation of aqueous solution. PVA could be a good candidate for incorporation into
multilayer coatings for encapsulation of organic solar cells. Despite the fact that PVA does not absorb radiation of
wavelengths longer than 300 nm, PVA is sensitive to photooxidation. It is well admitted that degradation can be
initiated by chromophoric impurities or defects, which absorb UV light and produce radicals that react further with
the polymer by hydrogen abstraction. Few papers deal with the photochemical behaviour of PVA, most of them
being limited to the fate of PVA irradiated at short wavelength (254 nm). Even if PVA is considered as a photostable
polymer (compared to polyolefins for example), in presence of light and oxygen, PVA degrades and the chemical
modifications induced by the various photochemical reactions lead to the loss of its physico-chemical properties.
PVA with different hydrolysis percentages are commercially available (between 70 and 99 %), and we report here
the photochemical behaviour of PVA hydrolysed at 98%. A comprehensive mechanism of PVA photo oxidation can
be proposed thanks to several analytical tools that permit the identification of the many photoproducts formed4,5,6.
There are two potential sites of hydrogen abstraction: either at the tertiary carbon atom (C1) or at the secondary one
(C2). The hydrogen abstraction followed by oxygen fixation and subsequent hydroperoxide decomposition lead to
the formation of macroalkoxy radicals. These radicals can undergo β-scission of the C-O bond or of the C-C bond.
The successive hydrogen abstraction on the C1 and the C2 carbon atom allows for the formation of the
macromolecular and molecular products that can be detected and identified using several analytical techniques,
which include infrared and UV-visible spectroscopies, XPS, SPME.

    OH
CH2 CH CH2 CH
0.98 O 0.02

C O
CH3

SCHEME 1: Structure of PVA

“Light-Absorbing” Polymers: The Example of MDI-Based Polyurethane,

Poly(N-Vinylcarbazole) (PVK) and Poly(3-Hexylthiophene) (P3HT)

The direct absorption of UV-visible light by the chromophors of the polymeric matrix may be responsible for
photophysical processes and direct photochemical reactions. Under the impact of light, aromatic polymers can
undergo various reactions, such as rearrangement (photo-Fries reactions), chain scissions or cross-linking without
involvement of oxygen. Photo-Fries rearrangements have been reported in the case of bisphenol-A polycarbonate7 or
aromatic MDI-based polyurethanes (see Mechanism II in Scheme 2). Norrish reactions were reported in the
literature to be involved in the phototransformation of polymers with carbonyl groups in their structure. The
involvement of Norrish reactions was extrapolated to the case of polymers with ester functions, but this last issue is
controversial8.

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Polyurethanes based on aromatic diisocyanates rapidly degrade and undergo yellowing on exposure to UV light.
Numerous studies have then concerned the UV induced photo-yellowing and the photochemical processes
responsible for the photodiscolouration of these materials. It is generally admitted that the yellowing of
polyurethanes based on 4,4'-diphenylurethane diisocyanate (MDI) involves two main pathways corresponding to the
mechanisms I and II shown in scheme 29. Mechanism I involves a classical chain oxidation initiated by hydrogen
abstraction on the methylene followed by fixation of oxygen and formation of hydoperoxides. Hydroperoxides are
photochemically and thermally unstable and decompose to give macroalcoxy radicals and hydroxyl radicals. Both
these radicals are likely to initiate new reactions by hydrogen abstraction on the macomolecular backbone.
Macroalcoxy radicals may decompose by several routes that involve β-scission reactions, leading to several
carbonylated photoproducts.
Mechanism I

O C NH CH2 NH C O
O O

hν, O2 Mechanism II

O C NH hν CH2 NH2
CH2 NH C O
O O
O C N C N C O CO
O O O

SCHEME 2: Mechanism responsible for the photoyellowing of MDI-based PUR

Polycarbazole copolymers could be promising candidates for applications in the domain of organic photovoltaic
cells (OPV), because they are known to be more stable in air and capable of withstanding high temperatures for
extended periods of time.
  C H2 CH

SCHEME 3. Structure of poly(N-vinylcarbazole) (PVK).

In the absence of oxygen, the absorption by PVK of light in the range of wavelengths of solar radiations (λ > 300
nm) provokes scission of the N-C bond, which gives a carbazolyl radical and a macroalkyl radical. Abstraction of
hydrogen by the carbazolyl radical leads to the formation of molecular carbazole that is trapped in the irradiated
film. Abstraction of a hydrogen atom preferentially occurs on tertiary carbon atoms of the macromolecular chains
structure, leading to a polycarbazolyl radical. These radicals formed simultaneously might recombine, leading to
cross-linking10. In the presence of oxygen, these various radicals react in a classical chain oxidation mechanism.

Poly(3-hexylthiophene) (P3HT) is a very popular active material for organic solar cells as it was among the most
efficient compounds until these last years.
C6H13

S
n

SCHEME 4: Chemical structure of P3HT

The UV-visible absorption spectrum of pristine P3HT has a broad absorption band in the visible, which is indicative
of an extensive π-electron delocalisation. The spectrum is well structured with resolved features at 520, 550 and 600
nm, this latter structure being assigned to interchain absorption coming from highly ordered domains.
Photooxidation alters the degree of interchain order in the microcrystalline domains of P3HT, as evidenced by the
progressive disappearance of the shoulder at 600 nm, and provokes the formation of several new absorption bands,
detected by IR spectroscopy in the carbonyl, hydroxyl and fingerprint regions. The main degradation products that
were identified were classed into two main families: carbonyl and sulfur-containing moieties. The comparison of the
photooxidation of P3HT and polythiophene showed that polythiophene was rather photostable. This instability of
P3HT under light exposure can be related to the oxidizability of the carbon atom in the α position to the thiophene

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ring11. Indeed, a major parameter controlling the reactivity in free-radical reactions is the energy of the bonds being
broken and the stability of the radical formed. The abstraction of a labile hydrogen atom on the CH2 group in the α
position to the ring of P3HT is then strongly favoured as the resulting macroradical is stabilized by conjugation with
the thiophenic system. A degradation pathway involving the radical oxidation of the n-hexyl side chains and the
subsequent stepwise oxidation of the sulphur atom of the thiophene ring oxidation of the side chain by ground-state
oxygen has been proposed. The oxidation proceeds via a free-radical chain reaction route that involves hydrogen
abstraction from the substituents, thus forming carbonyl and hydroxyl adducts, and may include crosslinking. This
result confirms that the weak point of P3HT is the hexyl substituent. The breaking of the macromolecular backbone
results in a loss of π-conjugation, provoking the bleaching of the sample.

REFERENCES

1
J.L. Gardette, Fundamental and technical aspects of the photoageing of polymers, in Handbook of Polymer Degradation (Editor
S. Halim Hamid), Marcel Dekker, 2000, 671-698
2
J.L. Gardette, A. Rivaton, S. Morlat-Therias, B. Mailhot, Fundamental and technical aspects of the photoageing of polymeric
materials, in Service Life Prediction (Editors J.W. Martin, R.A. Ryntz, R.A. Dickie), Federation of Societies for Coatings
Technology, 2005, 275-286
3
J.L. Gardette, A. Colin, S. Trivis, S. German, S. Therias, Impact of photooxidative degradation on the oxygen permeability of
poly(ethyleneterephthalate), Polym Degrad Stab 2014; 103: 35-41
4
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5
M. Gardette, A. Perthue, J.L.Gardette, T. Janecska, E. Foldes, B. Pukanszky, S. Therias, Photo- and thermal-oxidation of
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6
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monitor polypropylene photodegradation?, Polym Degrad Stab, 2016; 128: 200-208
7
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of bisphenol-A polycarbonate and trimethylcyclohexane-polycarbonate, Polym. Degrad. Stab, 2002; 75: 17-34
8
S. Therias, J.F. Larché, P.O. Bussière, J.L. Gardette, M. Murariu, P. Dubois. Photochemical Behavior of Polylactide/ZnO
Nanocomposite Films. Biomacromolecules, 2012; 13(10): 3283-3291
9
C. Wilhelm, A. Rivaton, J.L. Gardette, Infrared analysis of the photochemical behavior of segmented polyurethanes. Part 3:
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10
A. Rivaton, B. Mailhot, S.Robu, M. Lounaci, P.-O. Bussière, J.L.Gardette, Photophysical processes and photochemical
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11
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cells active layer, Solar Energy Materials and Solar cells 2011; 95: 1315-1325

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