Heteroatom chain polymers, biodegradable

For ease of discussion, this section is divided into three broad classifications — natural, synthetic, and modified natural based biodegradable polymers and plastics. Natural polymers indicate no modification of isolated polymer, synthetic poisoners include carbon chain and heteroatom chain polymers, and modified natural polymers encompass grafts and blends, and chemical modifications such as oxidations and esterifications. 

Biodegradable polymers and plastics are readily divided into three broad classifications (/) natural, (2) synthetic, and (J) modified natural. These classes may be further subdivided for ease of discussion, as follows (/) natural polymers (2) synthetic polymers may have carbon chain backbones or heteroatom chain backbones and (J) modified natural may be blends and grafts or involve chemical modifications, oxidation, esterification, etc. 

Heteroatom Chain Backbone Polymers. This class of polymers includes polyesters, which have been widely studied from the initial period of research on biodegradable polymers, polyamides, polyethers, polyacetals, and other condensation polymers. Their linkages are quite frequendy found in nature and these polymers are more likely to biodegrade than hydrocarbon-based polymers. 

In contrast to many other polymers classified as biodegradable, PVA exhibits a backbone solely made up of carbon. The presence of a heteroatom like O or N in the main chain is definitely not a prerequisite for Nature to handle a polymeric structure that does not exist in nature. PVA degradation starts with random oxidations of the polymer backbone in the extracellular or periplasmic space of some microbes. Specific enzymes able to detect such sites of first attack continue in a hydrolytic way, yielding ever smaller polymer fragments that finally can be metabolised by the microbe or the microbial community. 

It is very difficult, if not impossible, to extrapolate the appearance of ecotoxic degradation metabolites or residues exclusively from the chemical structure of a polymer. Nevertheless, some basic guidelines concerning the presence (or absence) of heteroatoms and aromatic compounds in the polymer chain can be followed. The use of combined tests for biodegradability and ecotoxicity is strongly recommended. 

In this chapter we have shown that studies of the thermodynamics and kinetics of ROP play an indispensable role in our understanding of polymerization mechanisms. The results of these investigations have helped to establish controlled polymerization conditions, allowing the preparation of polymers with required molar masses and microstructures. The presence of various heteroatoms within the macromolecular main chain introduces an almost infinite number of possible homopolymeric and copolymeric properties. A recent development has been the controlled synthesis of aliphatic polyesters, mostly via ROP, based on their potential applications as biodegradable thermoplastics or as biomedical polymers. Moreover, as some cyclic ester monomers are prepared from renewable resources, some of the examples provided here have related to the ROP of aliphatic cyclic esters. 

---