R. Arnaud et al., PHOTOOXIDATION AND BIODEGRADATION OF COMMERCIAL PHOTODEGRADABLE POLYETHYLENES, Polymer degradation and stability, 46(2), 1994, pp. 211-224
Representative samples of commercial photodegradable polyethylenes hav
e been examined with respect to rate and extent of oxidation as measur
ed by carbonyl (carboxylic acid and ester) formation, molar mass reduc
tion and ability to support microbial growth when used as the only sou
rce of carbon. An ethylene-carbon monoxide (E/CO) copolymer was found
to photodegrade most rapidly but to biodegrade most slowly. An antioxi
dant iron dithiocarbamate photodegradable polyethylene (Scott-Gilead)
and a starch filled iron catalysed polyethylene were shown to produce
more carboxylic acids during photooxidation than did the E/CO polymer,
resulting in more rapid microbial growth. After removing the microorg
anisms, the surface of the oxidised polyethylene was found to be erode
d with substantial reduction in sample thickness, while the molar mass
of the polymer remained unchanged. It is shown that the microbial exo
enzymes are able to recognise relatively high molar mass carboxylic a
cids and remove them from the surface of the polymer under conditions
where water is not able to remove them by leaching. From this it is co
ncluded that the oxidation products of oxidised polyethylene are unlik
ely to present a threat to the environment and that by conversion to b
iomass they contribute to the fertility of the soil. Abiotic iron cata
lysed photo- or thermooxidation is the rate-limiting step in the bioas
similation process. It is concluded that abiotic oxidation must preced
e the onset of biotic degradation, which is shown to occur readily at
M(w) as high as 40 000. Bioassimilation involves further oxidation cat
alysed by transition metal ions and probably by exo enzymes from the m
icroorganisms.