Thermo-/photo-oxidation products

A particularly relevant thermo-oxidative study on PET degradation and PBT reported the degradation products observed for ethylene dibenzoate [39], The products observed paralleled those of the photolysis and photo-oxidation reports discussed above with benzoic acid, vinyl benzoate, 2-hydroxyethylene dibenzoate, 2-carboxymethoxy benzoate and the coupling product, 1,4-butylene dibenzoate, being reported. The 2-hydroxyethylene dibenzoate and 2-carboxymethoxy... 

Polyethylene oxide) (PEO) is a semicrystalline water-soluble polymer [64, 65], with a crystallinity that is very sensitive to the thermal history of the sample, making this property interesting as an indicator of degradation. Because it is biodegradable and biocompatible, PEO is a good candidate for environmental and medical applications [66-68]. The mechanisms of thermo- and photo-oxidation of PEO have already been investigated [69, 70] on the basis of IR identification of the oxidation products and are summarized in Scheme 10.1. 

Figure 3.3 Volatile degradation products in two oxidized polymers monitored by head-space GC. (a) Photo-oxidized LDPE with iron dimethyl dithiocarbamate and carbon black 1 = acetaldehyde 2 = methanol 3 = acetone 4 = 1-butanol 5 = butanol 6 = 3-pentanol. (b) Thermo-oxidized nylon 66 1 = acetaldehyde 2 = Cu-acetate 3 = cyclopentanone 4 = aniline.

The macro radicals formed by HPD will be in close proximity and would not be rapidly separated by diffusion, while the cage reaction between them would yield the identified products and confirm some experimental data on the accumulation of functional groups during photo-oxidation (Fig. 3) or thermo-oxidation (Fig. 4). 

The stabilization mechanism of HAS on photo- and thermo-oxidation was attributed to the HAS as such with a more or less pronounced contribution of their oxidation products [39]. For example, high molecular weight HAS protects from thermal oxidation even in the absence of their oxidation products and at temperatures as high as 135°C. Tensile strength, carbonyl index, and other properties vary with aging time without significant induction period (Fig. 1). 

Transformation products of phenolic antioxidants act differently and in many cases contrary to under photo- and thermo-oxidative conditions, also influencing the efficiency of stabilizer mixtures in different ways. Phenol-HAS mixtures also behave synergetically during thermo-oxidation, but show antagonistic effects during photo-oxidation. 

One of the reasons for that is the high stability of the O-H bond in the newly formed silanol group (125-130 kcal/mol), and H-r can be not only a hydrocarbon molecule, but also H-OH, H-NH2, etc. The diamagnetic dioxasily-rane groups are also the generators of alkyl radicals (see subsection 4.2). Many intermediates can be obtained as the products of thermal or thermo oxidative transformations or photo transformations of other initial structures. For example, vinoxyl radicals were obtained by the photolysis of peroxide radicals of the vinyl type [119] ... 

Crystalline starch beads can be used as a natural filler in traditional plastics [3]. They have been particularly used in polyolefins. When blended with starch beads, polyethylene films biodeteriorate upon exposure to a soil environment. The microbial consumption of the starch component leads to increased porosity, void formation, and loss of integrity of the plastic matrix. Generally, starch is added at fairly low concentrations (6-15 wt%). The total disintegration of these materials is obtained using transition metal compounds, soluble in the thermoplastic matrix, used as pro-oxidant additives to catalyze the photo and thermo-oxidative processes [4]. These products belong to the first generation of degradable polymers that biodeteriorate more than mineralize to CO2 and H2O in a time... 

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