2

PHOTOCHEMISTRY
2.1 GENERAL PRINCIPLES
An excited molecule may:
change into a different electronic state (see Chapter 1)
absorb more energy
change into a different compound (photochemical reaction)
t ransf er energy t o anot her mol ecul e or segment of t he exci t ed mol ecul e
(sensitizerquencher)
Adiscussion of photophysical changes is included in Chapter 1. Absorption of additional
energy is governed by principles similar to absorption of the first quantum (there are
some exceptions). Two different mechanisms exist in multiphoton excitation. In one, a
species may absorb the energy of one photon, andduring the lifetime of excitation(10
-4
to
10
-9
s) may absorb the energy of a second photon or more photons. Such excitation is
called resonant excitation. The other excitation process is called non-resonant excita-
tion; inthis process a second photonmust arrive almost simultaneously (withinthe time
frame of one cycle of electromagnetic radiationor 10
-15
s). The intensity of radiationmust
be very high for any reasonable probability of such sequential acts. When resonant exci-
tation occurs, the molecule in an excited state may change its properties which deter-
mine its capability to further absorb radiation of a particular wavelength (its absorption
may differ from the wavelength absorbed by the molecule in its original state). In both
cases the Beer-Lambert Law does not hold.
Electronically excited species (single or multiphoton) may possess sufficient energy
to dissociate. In complex molecules, the optical dissociation usually does not play an es-
sential role because such molecules are populated by a large number of electronic states
and vibrational modes which favor radiational transitions between the states. Fig. 2.1
shows the various states of molecules. Horizontal lines show quantized vibrational en-
ergy levels. At the minimumpotential energy level (minimumon graph) bond distances
Artificial weathering versus natural exposure 25
are normal. Moving towards the left from the mini-
mum (towards y axis) the molecular bond becomes
compressed (the bond is under compressive stress),
and, moving towards the right from the minimum,
the bond becomes extended (the bond is under ex-
tension stress). Bonds which are either extended or
compressed have an increased probability of under-
going a chemical conversion. This is especially true
when the bond is excessively extended (the nuclear
distance is large) and the bond is broken.
In the absence of molecular collisions or inter-
nal conversion, excited organic molecules will re-
main in an excited state for a particular time
(radiative lifetime) and then dispose of their energy
through spontaneous emission. The prevalent reac-
tions are those which lead to configurational
changes or those which involve several molecules or
groups in one segment of a molecule.
2.2 PRIMARY PHOTOREACTIONS
2.2.1 CLEAVAGE INTO FREE RADICALS
Aspecies containing one or more unpaired electrons is called a free radical. The stability
of free radicals varies and includes some very stable species such as the oxides of nitro-
gen. The stability of radicals can be increased by resonance, hyperconjugation, steric
hindrance, etc. Another distinctive feature of free radicals is their paramagnetic prop-
erty. According to Paulis Principle, any two electrons occupying the same orbital must
have opposite spins in order to maintain a total magnetic moment of zero. Free radicals,
however, have one or more unpaired electrons therefore, their net magnetic moment is
different fromzero. This property is important because it allows us to detect and distin-
guishfree radicals by electronspinresonance, ESR, measurement. Free radicals are the
only species giving ESR spectrum which might be used for both quantitative and quali-
tative studies. UV radiation present in sunrays has enough energy to cause bond cleav-
age and generate free radicals.
Several mechanisms of bond cleavage are known, but Norrish type cleavages of
type I and II are the ones most applicable to macromolecular materials. The n* sin-
glet-singlet transitions (forbidden) in aldehydes and ketones are responsible for their
UV absorption in the 230 to 330 nm region. The absorption band lies near 290 nm for
aliphatic aldehydes and near 280 nm for ketones. In aromatic substitution, this band is
shifted to longer wavelengths (in benzophenone near 340 nm). This helps to explain the
26 G. Wypych
Fig. 2.1. Energy states of molecule.
properties of some materials. For example, aliphatic polyurethanes are known to de-
grade rather rapidly with a simultaneous decrease in carbonyl absorption whereas aro-
matic polyurethanes exposed to UV radiation, accumulate carbonyl groups but do not
degrade (apparently the energy at the shifted wavelength (340 nm) is not sufficient to
cause bond cleavage). The cleavage of ketones to two radicals, called Norrish type I
cleavage, is explained by the following equation:
The secondary process of this cleavage yields carbon monoxide and R
.
radical. Norrish
type I reactions occur with aldehydes and ketones as well as carboxylic acids, their es-
ters, and their amides. Several other bonds cleave according to the Norrish type I mech-
anism:
Aliphatic azo compounds degrade according to the same mechanism, sometimes
called photoextrusion:
The first step is trans to cis isomerization, followed by elimination of nitrogen from
the compound. The other extrusion reaction involves aldehydes:
causing carbon monoxide to be lost by the molecule. This reaction applies only to alde-
hydes. Although the ketone reaction gives the same result, ketones require the forma-
tion of two radicals which then can recombine, whereas in the case of aldehydes the first
step requires proton migration followed by expulsion of CO. These reactions are temper-
ature dependent. At lower temperatures, less vibrational energy is available, therefore
Artificial weathering versus natural exposure 27
the efficiency of decarbonylationis greatly reduced. Insolution, vibrational energy dissi-
pates rapidly, consequently, decarbonylation is reduced.
The Norrishtype II cleavage involves abstractionof -hydrogenandbondcleavage:
This mechanism applies to aldehydes and ketones of both singlet and triplet n*
states having -hydrogen. Esters, anhydrides and other carbonyl compounds can also
follow this path. Aliphatic ketones undergo reactions from both singlet and triplet
states, whereas the reactions of aromatic ketones may start fromtriplet state only. Both
Norrish type I and II mechanisms depend on radiation wavelength. As wavelength de-
creases, most ketones produce an increasing amount of CO. Both Norrish mechanisms
involve the homolytic cleavage which results in a radical pair or, if a cyclic compound is
involved, a diradical. Heterocyclic cleavage produces an ion pair or a zwitterion:
2.2.2 ABSTRACTION OF HYDROGEN
The Norrish type II mechanism occurs in the first stage of the reaction. The
intermolecular Norrish type II hydrogen abstraction occurs easily when a cyclic
six-membered transition state is not precluded by transition states, whereas three- and
four-membered transition states are highly unfavorable.
The hydrogenabstractioncanbe anintramolecular or anintermolecular processes.
Both processes are typical of molecules in the two lowest excited states (n,*). Aryl ke-
tones normally react through a triplet state, and such reactions are not stereospecific.
Alkyl ketones react via both singlet and triplet states, and only the singlet reaction is
stereospecific. In their excited state, ketones act as if they were radicals, and thus they
are capable of very effective hydrogen abstraction.
Inanintramolecular abstractionroute, similar to the Norrishtype II mechanism, a
biradical is generated which may recombine forming the cyclic compound. This reaction
is typical of many photochemical processes whichleadto degradationor synthesis of ma-
terials. The efficiency of intermolecular abstraction of hydrogen depends on steric hin-
drance.
Many photochemical reactions occur throughanintramolecular route. Here, a good
donor of hydrogen must be present (saturated hydrocarbons are not efficient donors be-
28 G. Wypych
cause slightly weaker hydrogen bonding is required in the donor - this exists in com-
pounds which have electron-withdrawing groups in the -position). The irradiation of
ketones in the presence of hydrogen donors, such as amines, alcohols, hydrocarbons,
etc., results in hydrogen abstraction:
Benzophenone is a well known photosensitizer:
The efficiency of this reactiondecreases as temperature increases. Ketyl radicals formed
in this process can participate in secondary recombination reactions leading to pinacols
(see below under photodimerization).
Ketones are not the only compounds able to abstract hydrogen. Other examples in-
clude azobenzene and nitrobenzene, both of which can abstract hydrogen fromisopropyl
alcohol:
The presence of a double bondinthe molecule contributes to hydrogenabstraction:
Artificial weathering versus natural exposure 29
Alkenes, on photoexcitation, form a Rydberg state. In this state, they are able to ab-
stract hydrogen:
Finally, hydrogen can be easily abstracted by free radicals:
2.2.3 PHOTOADDITION REACTIONS
In photoaddition reactions, the Woodward-Hoffmann rule of conservation of orbital
symmetry applies. According to this rule, no change of orbital symmetry occurs on
transiting fromreactants to products. In other words, during the adiabatic transforma-
tion of the molecular orbitals of reactants to the molecular orbitals of products, no
change in symmetry occurs. Based on this rule, photochemical reactions differ from re-
actions which are thermally induced. In thermally induced reactions, the controtatory
mode is more energetically favored. But in photochemical reactions the disrotatory
mode is more favored. In most cases, this rule is confirmed by experiment. However,
some exceptions are known.
Numerous reactions are typical; some of the most common involve a condensation
mechanism forming cyclic compounds, hydroperoxides, dioxetanes, and addition of al-
dehydes and ketones (some are reported under photodimerization, e.g., Diels-Adler re-
action). Some of these routes might be useful in explaining crosslinking and secondary
mechanisms of radical degradation.
2.2.4 PHOTOISOMERISM
Two types of photochemical rearrangements cause isomerism: formation of structural
isomers and formation of valence-bond isomers. The first group is discussed in the next
section, and here we are concerned with formation of isomers without an actual dis-
placement of atoms or groups. The isomers are formed by the movement of electrons and
the change in the position of some nuclei. Photochemical changes of this nature can be
reversedby thermal energy. One example of photoisomerismfor azo compounds appears
above. Others are important in the understanding of the changes occurring in the mole-
cules during the photolytic process. Cis-trans isomerization is the most common exam-
ple. Cis-stilbene is an example of cis-trans isomerization:
30 G. Wypych
followed by cis-octyloctene:
Cis-trans conversions involve triplet states which are different for the cis and the
trans forms (there is no commonintermediate for cistrans and transcis conversions).
In the case of stilbene the transcis conversion is temperature and solvent dependent
whereas the cistrans conversion is independent of these. There is also a difference in
the amount of longer wave radiationthat eachisomer canabsorb (trans-stilbene absorbs
more energy). In photochemical isomerization, substantially more cis-stilbene is
formed. For conjugated dienes, these relationship will be reversed (the photochemical
conversion produces less of the cis form). One explanation is that the cis triplet state has
a lower energy than the trans triplet state (opposite to stilbene). The direction of
isomerization also depends on an absorbed wavelength (the amount of energy in the ab-
sorbed radiation) and on whether the process occurs directly or through a sensitizer (if a
sensitizer is involved, its type will affect the ratio of isomers).
These principles are important when considering photolytic changes. The nuclear
shape or geometry of electronically excited species are frequently different than that of
the ground state. This is not surprising, because the energy, the electronic configura-
tion, and possibly the electronic spin of an excited state, are different from those of a
ground state. These differences also exist between triplet and singlet states in the same
excited molecule. An excited molecule of cis-stilbene has perpendicular geometry, as
compared to the planar geometry of the cis-trans isomers. When an excited molecule re-
turns to the ground state, it canformeither of the two isomers. The probability of one be-
ing formed is determined by the above considerations. This helps us to realize that
molecules inexcited states have properties whichdiffer fromthose of their ground state.
Therefore, a reaction which would not be possible in the ground state, because of the
steric hindrance, may occur in the excited state. On the other hand, one should also take
into consideration the Franck-Condon Principle:
Artificial weathering versus natural exposure 31
Since electronic motions are much faster than nuclear
motions, electronic transitions occur most favorably when
the nuclear structure of the initial and final states are most
similar.
Whenanelectronis ina lower vibrational level thanthat whichcancause cleavage,
bond scission can still occur because the bond finds itself in a compressed position and,
when retracted by an outward surge, the bond may break.
Double bond isomerizationalso occurs. Inthe case of olefins, double bond migration
was observed when UV radiation was employed in the presence of hydrogen bromide:
The possible mechanism of double bond migration involves a free-radical process.
The photo-Fries rearrangement discussed belowcan also be treated as a particular case
of photoisomerization.
2.2.5 INTRAMOLECULAR REARRANGEMENT
When a molecule absorbs radiation it changes geometry, as explained above, and this
creates conditions for many possible rearrangements to occur. If an excited molecule
loses its natural rigidity, it becomes more flexible which results in a higher probability
that its structural element could come into sufficient proximity to exchange elements of
their structure. This is the reason for numerous rearrangements occurring - some of
them discussed above as photoisomerization.
The photo-Fries rearrangement explains photolytic changes in several polymers.
The reaction is predominantly a free-radical process described by the following equa-
tion:
32 G. Wypych
It can be seen that the reaction changes the structure of the backbone of polymers and
forms reactive groups which did not exist before. A similar reaction occurs when
acylated arylamines are exposed to UV radiation:
which in turn releases a free amine group - changes relevant in the case of polyamides
and polyurethanes. Many other similar reactions are possible. In some, halogen-con-
taining protonic acids participate:
which introduces a new substituent to the aromatic structure.
Intermolecular rearrangement reactions, when divided into sigmatropic,
electrocyclic, andstructural rearrangements helpto explainthe formationof conjugated
segments and various cyclic compounds found in degradation products of polymeric ma-
terials.
2.2.6 PHOTODIMERIZATION
Artificial weathering versus natural exposure 33
Awell-known sensitizer - benzophenone - when irradiated in the presence of a hydrogen
donor (e.g., alcohol), dimerizes according to the following reaction:
A reaction of a similar type may lead to Diels-Adler condensation products:
or other structures of unusual geometries:
some of which are useful in explaining the peculiarities of various degradation mecha-
nisms.
34 G. Wypych
2.2 7 PHOTOREACTIONS
The list below includes some common photolytic reactions:
2.3 SECONDARY PHOTOREACTIONS
From the brief discussion of primary photoreactions above, one may deduce that they
multiply into a wide variety of secondary processes which are material specific which
should be discussed as specific cases. One type of reaction(primary or secondary) is com-
mon for all materials - namely, photooxidation - and this reaction is the only one dis-
cussedhere. Molecular oxygennormally exists inits triplet state (
3

g
\
). Of the two singlet
Artificial weathering versus natural exposure 35
Table 2.1: Sources of singlet oxygen
Electrical discharge
Microwave discharge
Chemical sources - reactions:
hydrogen peroxide and hypochlorite ion
alkaline hydroperoxide
decomposition of sec-butylperoxy radicals
decomposition of superoxide ion
decomposition of transition-metal-oxygen complexes
decomposition of products reacted with ozone
Photolysis:
direct formation
heating of peroxides formed during photolysis
states, (
1

g
and
1

g
+
), only one, (
1

g
), is ina highly
reactive form but the second, (
1

g
+
), may rapidly
relax to
1

g
with the liberation of 15 kcal/mol en-
ergy. Sources of singlet oxygen are given in Ta-
ble 2.1.
The lifetime of singlet oxygen is relatively
long because the conversion to its ground state
triplet requires spin change. Temperature has
some effect on singlet oxygen lifetime but it is
most dependent on the environment (Table 2.2).
The presence of hydrogen in the solvent mole-
cule considerably reduces singlet oxygen life-
time. Singlet oxygen is an important factor in
the photooxidative process of polymer films be-
cause of its large mean diffusion path (115 )
and its relatively long lifetime (half-life of 5x10-2 s at atmospheric pressure).
36 G. Wypych
Table 2.2: Lifetime of singlet
oxygen,
1

g
, in various solvents
Solvent Lifetime, s
H
2
O 2
CH
3
OH 7
benzene 24
CH
3
COCH
3
26
CHCl
3
60
CS
2
200
CCl
4
700
Singlet oxygen reactivity is characterized by the following reactions:
The most important species which can react with singlet oxygen are unsaturations,
aromatic rings, and radicals.
Artificial weathering versus natural exposure 37