Polymer degradation scissions

The role of cavitation in ultrasound degradation has been confirmed repeatably in most experiments where cavitation was prevented, either by applying an external hydrostatic pressure, by degassing the solution, by reducing the sound intensity or the temperature, polymer chain scission was also largely suppressed [117]. 

Well before the advent of modern analytical instruments, it was demonstrated by chemical techniques that shear-induced polymer degradation occurred by homoly-tic bond scission. The presence of free radicals was detected photometrically after chemical reaction with a strong UV-absorbing radical scavenger like DPPH, or by analysis of the stable products formed from subsequent reactions of the generated radicals. The apparition of time-resolved ESR spectroscopy in the 1950s permitted identification of the structure of the macroradicals and elucidation of the kinetics and mechanisms of its formation and decay [15]. 

The second phase of polymer degradation is characterized by a decrease in the rate of chain scission (Fig. 19) and the onset of weight loss. Weight loss has been attributed to (1) the increased probability that chain scission of a low molecular weight polymer will produce a fragment small enough to diffuse out of the polymer bulk and (2) the breakup of the polymer mass to produce smaller particles with an increased probability of phagocytosis. The decrease in the rate of chain scission, as well as the increased brittleness of the polymer, is the result of an increase in the crystallinity of PCL,... 

Some polymers degrade readily when heated to the processing temperature by bond scission. In contrast, if the polymer has a completely aromatic structure (e.g., PES, PEEK) the thermal stability is high (greater than 400°C for short... 

Pyrolysis GC/MS is limited in application to those studies in which the compounds formed are capable of being analysed by GC, that is it is only reasonably suitable for low molecular weight products. Many synthetic polymers degrade (pyrolyse) by processes that may simply be described as either random scission (e.g., polyolefins), unzipping to produce mostly monomers (e.g., PMMA)... 

Polymer degradation typically occurs via random chain scission, depolymerization, or both, resulting in a loss of chain length and properties associated with polymer length. 

T. Sawaguchi and M. Seno, Thermal degradation of polyisobutylene effect of rotational motion around C-C- bond on the /1-scission leading to monomer formation, Polym. Degrad. Stab., 54(l) 23-32, October 1996. 

Staggs, J. E. J. Modelling random scission of linear polymers. Polymer Degradation and Stability 2002 76 37. 

Kostoglou, M. Mathematical analysis of polymer degradation with end-chain scission. Chemical Engineering Science 2000 55 2507. 

The types of polymer degradation can be divided into three general categories chain depolymerisation, random scission and substituent reactions. 

To remove the polymeric binder, the green body is heated often in an oxidizing atmosphere. During this process the polymer degrades along many possible degradation pathways, which include (1) scission of the main chain, (2) reaction with side chains and substituents, and... 

End-chain scission the polymer is broken up from the end groups successively yielding the corresponding monomers. When this polymer degrades by depolymerization, the molecules undergo scission to produce unsaturated small molecules (monomers) and another terminal free radicals. (Polymethylmethacrylate, polytetrafluorethylene, polymethacrylonitrile, polyethylstyrene, polystyrene, polyisobutene)... 

Thermal polymer degradation is determined by the chemical structure and length of the polymer chain, by the presence of unstable structures (such as impurities or additives) and by the temperature level inside the reactor, which must be high enough to break the weakest, primary chemical bonds. Madorsky and Straus [39] found that some polymers (such as PMMA and PTFE) mainly revert to their monomers upon heating, while others (such as PE) yield a great many decomposition products. These two types of dominant thermal polymer degradation are called end-chain scission and random-chain... 

---