Chemical transformation is the other most important parameter in the abiotic
degradation. Atmospheric pollutants and agrochemicals may interact with polymers changing the macromolecule properties [22]. Among the chemicals provoking
the degradation of materials, oxygen is the most powerful. The atmospheric form
of oxygen (i.e., O2 or 0 3) attacks covalent bonds producing free radicals. The
oxidative degradation depends on the polymer structure (e.g., unsaturated links
and branched chains) [23}. These oxidations can be concomitant or synergic to
light degradation to produce free radicals. Like the products ofNorrish reactions,
peroxyl radicals resulting of the oxidative degradation can lead to crosslinking
reactions and/or chain scissions.
Hydrolysis is another way by which polymers can undergo chemical degradation
[24 - 26]. Hydrolysis is dependent on parameters as water activity, temperature,
pH and time.
PLA degradation occurs in the presence of water provoking a hydrolysis of the
ester bonds. De Jong et al. [27] observed PLA depolymerisation by a progressive
release of dimers in alkaline conditions (Fig. 8.4). The end-chain degradation
may be explained by an intramolecular transesterification. An electrophilic attack,
catalyzed by a base, of the hydroxyl end-group on the second carbonyl group
leads to a ring formation. The polymer is shortened by the hydrolysis of the
resulting lactide. In a second step, the free lactide is hydrolysed into two molecules of LA. The intramolecular degradation occurs by a random alkaline attack on the
carbon of the ester group, followed by the hydrolysis of the ester link. Thus, new
molecules with low molecular weight are produced. In acidic conditions [28]
(Fig. 8.3), the protonation of the hydroxyl end-group forms an intramolecular
hydrogen bond. The hydrolysis of the ester group allows the release of a lactic
acid molecule leading to the decrease of the degree of polymerisation of the PLA.
An intramolecular random protonation of carbon in the ester group conduces also
to the hydrolysis of ester linkages. This hydrolysis gives different fragments of
lower molecular weights
Chemical transformation is the other most important parameter in the abioticdegradation. Atmospheric pollutants and agrochemicals may interact with polymers changing the macromolecule properties [22]. Among the chemicals provokingthe degradation of materials, oxygen is the most powerful. The atmospheric formof oxygen (i.e., O2 or 0 3) attacks covalent bonds producing free radicals. Theoxidative degradation depends on the polymer structure (e.g., unsaturated linksand branched chains) [23}. These oxidations can be concomitant or synergic tolight degradation to produce free radicals. Like the products ofNorrish reactions,peroxyl radicals resulting of the oxidative degradation can lead to crosslinkingreactions and/or chain scissions.Hydrolysis is another way by which polymers can undergo chemical degradation[24 - 26]. Hydrolysis is dependent on parameters as water activity, temperature,pH and time.PLA degradation occurs in the presence of water provoking a hydrolysis of theester bonds. De Jong et al. [27] observed PLA depolymerisation by a progressiverelease of dimers in alkaline conditions (Fig. 8.4). The end-chain degradationmay be explained by an intramolecular transesterification. An electrophilic attack,catalyzed by a base, of the hydroxyl end-group on the second carbonyl groupleads to a ring formation. The polymer is shortened by the hydrolysis of theresulting lactide. In a second step, the free lactide is hydrolysed into two molecules of LA. The intramolecular degradation occurs by a random alkaline attack on thecarbon of the ester group, followed by the hydrolysis of the ester link. Thus, newmolecules with low molecular weight are produced. In acidic conditions [28](Fig. 8.3), the protonation of the hydroxyl end-group forms an intramolecularhydrogen bond. The hydrolysis of the ester group allows the release of a lacticacid molecule leading to the decrease of the degree of polymerisation of the PLA.An intramolecular random protonation of carbon in the ester group conduces alsoto the hydrolysis of ester linkages. This hydrolysis gives different fragments oflower molecular weights
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