An overview of the literature together with selected authors' data on thermal and thermo-oxidative decomposition of commercial aliphatic nylons (nylon 6, nylon 7, nylon 11, nylon 12, nylon 6.6, nylon 6.10, nylon 6.12) is presented. Despite the high level of research activity and the large number of publications in the field, there is no generally accepted mechanism for the thermal decomposition of aliphatic nylons. Polylactams (nylon 6, nylon 11 and nylon 12) tend to re-equilibrate to monomeric or oligomeric cyclic products. Diacid–diamine type nylons (nylon 6.6, nylon 6.10 and nylon 6.12) produce mostly linear or cyclic oligomeric fragments and monomeric units. Because of the tendency of adipic acid to fragment with elimination of CO and H2O and to undergo cyclization, significant amounts of secondary products from nylon 6.6 are reported in some papers.

 Many authors have shown that the primary polyamide chain scission occurs either at the peptide C(O)NH or at adjacent bonds, most probably at the alkyl–amide NHCH2 bond which is relatively the weakest in the aliphatic chain. Hydrolysis, homolytic scission, intramolecular CH transfer and cis-elimination (a particular case of CH transfer) are all suggested as possible primary chain-scission mechanisms. There are no convincing results reported which tend to generally support one of these mechanisms relative to the others; rather, it seems that the contribution of each mechanism depends on experimental conditions. This conclusion is also supported by the wide spread of kinetic parameters measured under the different experimental conditions.

 More uniform results are observed in the literature regarding the mechanism of thermo-oxidative decomposition of aliphatic nylons. Most authors agree that oxygen first attacks the N-vicinal methylene group, which is followed by the scission of alkyl–amide NC or vicinal CC bond. Alternatively, it is suggested that any methylene group which is β-positioned to the amide group methylene can be initially oxidized. There are few mechanisms in the literature which explain discoloration (yellowing) of nylons. UV/visible active chromophores are attributed either to pyrrole type structures, to conjugated acylamides or to conjugated azomethines.

 Some secondary reactions occurring during the thermal or thermo-oxidative decomposition lead to crosslinking of nylons. Nylon 6.6 crosslinks relatively easily, especially in the presence of air, whereas nylon 11 and nylon 12 crosslink very little. Strong mineral acids, strong bases, and some oxides or salts of transition metals catalyse the thermal decomposition of nylons, but minimize crosslinking. In contrast, many fire retardant additives promote secondary reactions, crosslinking and charring of aliphatic nylons.

© 1999 Society of Chemical Industry

Thermal decomposition of aliphatic nylons

The faint emission of light by various classes and types of polymers when heated in the presence of oxygen, oxyluminescence, was studied by means of a photomultiplier tube and sensitive microammeter. Among the polymers with a carbon-carbon backbone, the polymers having the greater number of tertiary carbon atoms generally showed greater intensities of luminosity. Polystyrene was a notable exception to this generalization. The shape of the luminosity versus time curves varied with the type of polymer. It was also found that the emission of light did not stop instantly when the oxygen atmosphere was replaced by an inert gas, but rather followed an exponential type of decay. The rate of decay appeared to be different with different types of polymers. The intensities of luminescence and the times required to reach maximum or steady state luminescence were compared with oxygen uptake data for various polymers. In general there was a qualitative, but not necessarily quantitative correlation between the luminous intensities and polymer stabilities in the presence of oxygen.

Oxyluminescence of polymers. I. General behavior of polymers

Chemiluminescence from peroxides in polypropylene. Part I: Relation of luminescence to peroxide content

Analysis of test methods for UV durability predictions of polymer coatings

ConspectusBolland and Gee’s basic autoxidation scheme (BAS) for lipids and rubbers has long been accepted as a general scheme for the autoxidation of all polymers. This scheme describes a chain process of initiation, propagation, and termination to describe the degradation of polymers in the presence of O2. Central to this scheme is the conjecture that propagation of damage to the next polymer chain occurs via hydrogen atom transfer with a peroxyl radical. However, this reaction is strongly thermodynamically disfavored for all but unsaturated polymers, where the product allylic radical is resonance-stabilized. Paradoxically, there is no denying that the autocatalytic degradation and oxidation of saturated polymers still occurs. Critical analysis of the literature, described herein, has begun to unravel this mystery.One possibility is that the BAS still holds for saturated polymers but only at unsaturated defect sites, where H transfer is thermodynamically favorable. Another is that peroxyl termination rat...

/pdf/the-fate-of-the-peroxyl-radical-in-autoxidation-how-does-3vzjw382y3.pdf

The Fate of the Peroxyl Radical in Autoxidation: How Does Polymer Degradation Really Occur?

The oxyluminescence of polypropylene and polyethylene stabilized with various amounts of 4,4′-thiobis(3-methyl-6-tert-butylphenol) were studied and compared with oxygen uptake data. It was found that there was a correlation, although not linear, between the two methods. In the case of the stabilized polypropylenes, a pronounced aging effect was noticed. The oxyluminescent behavior of stabilized polyethylene was somewhat different from that of stabilized polypropylene. The temperature coefficients of the oxyluminescence of polypropylene, polyethylene, nylon 6, polystyrene, polyurethane and polymethyl methacrylate were obtained. From these data the apparent activation energies for the light-emitting reaction were calculated. For the olefin polymers, these values are close to the activation energies of the oxidative degradation reaction obtained by other means. Both polyethylene and polymethyl methacrylate have different activation energies below their transition points as compared to higher temperature, indicating a different mode of reaction in the solid state from that occurring in the melt. An interesting transition luminescence, which was more pronounced in the absence of oxygen, was observed in the case of polyethylene.

Oxyluminescence of polymers. II. Effect of temperature and antioxidants

The initial stages of isotactic polypropylene oxidation were investigated by oxidizing at 130°C. to various extents up to 10 ml. of oxygen consumed per gram of polymer. The development of infrared absorption bands in the carbonyl regions was followed, as increasing amounts of oxidation occurred. The oxidation uptake curves showed that both autocatalytic rate and induction time depended primarily on the thickness of the sample, contrary to the case of polyethylene. This indicated the initiation process was primarily diffusion controlled for samples of the thickness range studied. The presence of copper shortened the induction times and increased the autocatalytic rate. In this case, the dependency of the induction time on thickness was less. Dielectric data showed that polypropylene became unsuitable electrically at about the point where the autocatalytic oxidation set in. It was also found that the effects of prior exposure to oxidative conditions were cumulative to a considerable extent, and thus resulted in shorter induction times.

The early stages of isotactic polypropylene oxidation

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Oxyluminescence of polymers. I. General behavior of polymers

Oxyluminescence of polymers. II. Effect of temperature and antioxidants

The early stages of isotactic polypropylene oxidation